Property control of multifunctional surfaces

ABSTRACT

The physical and chemical properties of surfaces can be controlled by bonding nanoparticles, microspheres, or nanotextures to the surface via inorganic precursors. Surfaces can acquire a variety of desirable properties such as antireflection, antifogging, antifrosting, UV blocking, and IR absorption, while maintaining transparency to visible light. Micro or nanomaterials can also be used as etching masks to texture a surface and control its physical and chemical properties via its micro or nanotexture.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application claims priority to U.S. Provisional PatentApplication No. 62/532,857, filed on Jul. 14, 2017, and U.S. ProvisionalPatent Application No. 62/443,558, filed on Jan. 6, 2017, thedisclosures of both being incorporated herein by reference in theirentirety.

TECHNICAL FIELD

The present disclosure relates to multifunctional surfaces. Moreparticularly, it relates to methods to control surface properties bynanoparticle monolayers.

BRIEF DESCRIPTION OF DRAWINGS

The accompanying drawings, which are incorporated into and constitute apart of this specification, illustrate one or more embodiments of thepresent disclosure and, together with the description of exampleembodiments, serve to explain the principles and implementations of thedisclosure.

FIG. 1 is a schematic illustration of the covalent attachment ofnanoparticles (NP) to a substrate.

FIG. 2 illustrates an example of using an NP-SAM complex to modify thetopography of a surface through blocking.

FIGS. 3-6 illustrate examples of nanoparticles and substrates withdifferent functionalization.

FIG. 7 illustrates a working station with multiple fabrication steps.

FIG. 8 illustrates an exemplary surface that is transparent to visiblelight while blocking UV light.

FIG. 9 illustrates an exemplary surface for UV blocking and visiblelight transmission.

FIG. 10 illustrates an exemplary device to boost a solar cellefficiency.

FIG. 11 illustrates an exemplary available power as a function ofwavelength.

FIGS. 12-13 illustrate exemplary spectral efficiency for two cells.

FIG. 14 illustrates exemplary power enhancement.

FIG. 15 illustrates similar data as FIG. 13, but for a 15% efficiency Sicell.

FIG. 16 illustrates similar data as FIG. 14, but for a 15% efficiency Sicell.

FIG. 17 illustrates dark current-voltage (I-V) curves for a simulatedstructure.

FIG. 18 illustrates the power density for AM 1.5 G power.

FIGS. 19-20 illustrate current-voltage characteristics for a simulateddevice comprising a semiconductor with E_(g)=0.67 eV.

FIG. 21 illustrates an example of spacers between a solar cell and a topstructure.

FIG. 22 illustrates an exemplary concept of spectral efficiency atdifferent wavelengths.

FIG. 23 illustrates an exemplary simulation for the overall tandemefficiency.

FIG. 24 illustrates an exemplary structure with a PV panel and top andbottom absorbers.

FIG. 25 illustrates an array of conductive wires spaced apart andparallel to each other.

FIG. 26 illustrates an exemplary monolayer of microspheres and ananoparticle etching mask.

FIGS. 27-28 illustrate exemplary hierarchical structures.

FIGS. 29-30 illustrate an exemplary array of structures.

FIG. 31 illustrates exemplary elements that could be included in astructure.

FIGS. 32-35 illustrate exemplary photo absorption structures.

FIG. 36 illustrates solid applications.

SUMMARY

In a first aspect of the disclosure, a method is described, the methodcomprising: determining a first lateral dimension of each element in astructure on a surface, the structure comprising a plurality ofelements, the determining based on a first physical characteristic ofthe structure, the first lateral dimension being in a horizontalorientation relative to the surface; determining a second lateraldimension of each element, the second lateral dimension beingperpendicular to the first lateral dimension and in a horizontalorientation relative to the surface; determining a height of eachelement based on a second physical characteristic of the structure, theheight being in a vertical orientation relative to the surface;determining a spacing between the elements based on the first and secondphysical characteristics; and fabricating the structure.

In a second aspect of the disclosure, a method is described, comprising:determining a first lateral dimension of each element in a structure ona surface based on a desired transparency of the structure to incidentelectromagnetic radiations, the structure comprising a plurality ofelements, the first lateral dimension being in a horizontal orientationrelative to the surface and being less than half of a wavelength of anelectromagnetic radiation to be blocked by the structure; determining aheight of each element based on a desired reflectivity for the incidentelectromagnetic radiation, the height being in a vertical orientationrelative to the surface; determining a spacing between the elementsbased on the desired transparency and reflectivity; and fabricating thestructure.

In a third aspect of the disclosure, a structure is described, thestructure comprising: an array of pillars on a surface, each pillarhaving a first lateral dimension x, a second lateral dimension z, and aheight y; and a monolayer of particles covering each pillar, wherein xis between 50 nm and 250 nm, thereby blocking ultraviolet radiation, yis between 120 nm and 180 nm, thereby reducing reflected radiation, eachparticle of the monolayer has a diameter less than 200 nm and is made ofa material capable of absorbing infrared radiation.

DETAILED DESCRIPTION

Several existing products include coatings and other types of surfacemodifications to obtain particular physical, chemical, or electricalproperties for the product surface. For example, modification of surfaceproperties may be achieved by the deposition of nanoparticles on thesurface by a non-bonding process. These nanoparticles may be applied tothe surface by a spin, spray, or dip coating process. Nanoparticles maybe attached to surfaces for a variety of reasons, such as Ramanenhancement or to act as a catalyst. While these techniques, known tothe person of ordinary skill in the art, are effective in certainapplications, they nevertheless may present some drawbacks, mainly dueto the fact that these known techniques do not robustly attach thenanoparticles to the surface. Many of these known techniques also do nothave specificity, require extreme care during deposition, and do notgenerally attach a single layer of nanoparticles uniformly on a surface.Additionally, these processes may not be able to effectively apply asingle layer of nanoparticles onto curved or other non-uniform surfaces.

Alternatively, there are other methods known to the person of ordinaryskill in the art, in which nanoparticles are bonded to the surface. Forexample, nanoparticles can be bonded to one portion of a complementarybase pair of deoxyribonucleic acids (DNA), while the other portion ofthe complementary base pair is bonded to the surface. While thistechnique creates a single nanoparticle layer, there can beshortcomings. First, DNA denatures when it is heated; thus, thenanoparticle layer is not stable at high temperatures. Second, the DNAlinkage may not be chemically stable against strong acids/bases orextreme solvents. Third, attaching DNA to a particular substrate is avery complex process. Lastly, the raw materials for DNA attachment areexpensive.

The present disclosure describes methods to deposit monolayers ofnanoparticles with inexpensive and technologically less complextechniques, which allow for significantly increased control over thechemical and physical (e.g. optical and electrical) properties of theresultant surface coated with nanoparticles. Three dimensionalstructures with multiple levels and sizes of nanoparticles can also becreated using this technique. Therefore, while this technique describeshow to modify a surface with nanoparticles, the ability to coat multiplelayers of conformal and uniform particles enables not only theproduction of novel surfaces, but also enables the fabrication ofthree-dimensional materials and metamaterials as well.

In general terms, various methods disclosed herein are directed to theapplication of a single layer of nanoparticles on a substrate surface.The methods disclosed herein provide a stable and uniform coating on awide variety of surfaces (flat, curved, or non-uniform). In someembodiments, the size of the particles deposited can be in the nanometerrange, or in the micrometer range (e.g. microspheres). These particlescan be attached to a surface, for example, by different methods: 1.Inorganic bonding; 2. Organic bonding (click chemistry); 3. carefullycontrolled spraying or dipping. For example, fluids can be applied insuccessive, distinct steps to the particles and the surface, to createbonds or attraction between particles and surface. For example, a firstliquid can be sprayed or otherwise applied to the particles, while asecond liquid mixture can be applied to the surface, in distinct steps.Excess amounts of liquids can be removed, for example with a neatsolvent (or solvent mixture) or by drying. The first and second liquidsare chosen so as to be able to create a bond or attractive force betweenthe particles and the surface, creating a single uniform monolayer ofparticles on the surface. This technique can be modified to create morecomplex, hierarchical surfaces comprising multiple monolayers or otherstructures. A similar process can be carried out using organicchemistry. Instead of liquids, gases may be used. The fluids may also betermed “precursors”, as they prepare the different surfaces forsubsequent bonding (or attraction forces in general) between functionalgroups. In some embodiments, the particles (or particle suspension) areone of the two precursors. In this case, the particles can befunctionalized, rendering their surface reactive to the substrate,though in other embodiments the particles may be suitable for attractionupon being formed or fabricated. The particles can therefore be preparedin a separate step, to render them a precursor. The other precursor isapplied to the surface of the substrate. The particle precursor can thenattach to the surface treated with the other precursor. In other words,the process comprises the following steps: 1. The substrate is sprayedor otherwise prepared with a first precursor; 2. The substrate issprayed with a neat solvent or fluid mixture; 3. The substrate issprayed with a dispersion of particles (the particles are a precursorsuspended in a fluid); 4. The substrate is sprayed with a neat solvent.The precursors and solvents are chosen so as to allow the differentfunctional groups to interact, or not interact, as desired, in order toallow application of one monolayer while discouraging the attachment ofa second monolayer. Once the first monolayer is formed, the process canbe repeated, if necessary, to attach a second monolayer, and so forth.In other embodiments, the particles can be sprayed directly onto thesurface, relaying only on physical interactions, with no permanentbonds. For example, the particles may remain attached through van derWaals or electrostatic forces.

In some embodiments, functional groups like —OH and Al—CH₃ are used tobond particles to a surface. This approach is different from DNA-basedfunctionalization, because DNA methods are based on hydrogen bonds. Thecomplementary base pairs have hydrogen-type bonds. These hydrogen bondsdenature at high temperature. At high temperatures, the shape of the DNAstrands change and therefore the hydrogen bonding breaks up.

Examples of the nanoparticles used with the disclosed methods comprise,but are not limited to, metals, metal oxides, metal nitrides, carbonnanotubes, buckyballs (e.g. spherical fullerene molecules with theformula C₆₀), or architectured 3D nanostructures such as metal-organicframeworks (MOF).

Examples of the substrates used with the disclosed methods comprise, butare not limited to, glass, ceramics, plastics, polymers, textiles,semiconductors, metals, 3D printed materials, or 3D architecturedmaterials.

In some embodiments, a single, uniform layer of nanoparticles isdeposited on arbitrary surfaces by liquid phase atomic layer deposition.As known to the person of ordinary skill in the art, atomic layerdeposition (ALD) is a thin film deposition technique based on thesequential application of precursor components (e.g. two precursors),that are deposited on a substrate, where they chemically interact toform atomic bonds. ALD is considered a subclass of chemical vapourdeposition, as the precursors are generally introduced in the gas stateinside a deposition chamber. However, if the precursors are in theliquid state, the technique can be referred to as liquid phase atomiclayer deposition or solution atomic layer deposition (sALD), because theprecursors are dissolved in a noninteracting solvent.

In some embodiments, the layers are formed using a three-step process.In a first step, the nanoparticles are functionalized with “—OH” alcoholgroups. As the person of ordinary skill in the art will understand,there are many different chemical synthetic methods that can be used toattach “—OH” functional groups onto a nanoparticle of arbitrarycomposition (by way of example but not of limitation, the nanoparticlesmay comprise a pure metal or oxide). In a second step, the targetsubstrate (i.e., the surface that is to be coated) is exposed totrimethylaluminum (TMA) in a vacuum chamber, solution, or other methodsknown or developed in the art. In this second step, the substratesurface is functionalized with a “—CH₃” or methyl groups.

In a third step of this embodiment, the “—CH₃” functionalized substratecan be submerged in a bath of “—OH” functionalized nanoparticles. Thebath is composed of the functionalized nanoparticles suspended in anorganic solvent such as hexane (or other organic solvents that are freeof water or of reactive molecules which contain —OH groups). The methylgroups on the substrate surface react with the alcohol or, moregenerically, —OH group on the functionalized nanoparticles to form asubstrate-oxygen-nanoparticle (substrate-Al—O-nanoparticle) covalentbond, and a methane by-product (CH₄) (which exits the bath as adissolved gas, or bubbles out of the bath).

The covalent bond permanently attaches the nanoparticles to the surfacein a single layer. The attachment stops when all the “—CH₃” groups havebeen converted into covalent nanoparticle bonds. Subsequentnanoparticles that approach the surface may loosely adhere to thesubstrate, but they do not form covalent bonds. Accordingly, when thecoated substrate is removed from the bath and rinsed, the loosely boundnanoparticles will be removed, and the covalently bonded ones remain onthe substrate surface. In this way, it is possible to form a monolayerof covalently bonded nanoparticles, while any nanoparticle that possiblyattached as a second or third monolayer, etc. can be removed due to thefact that such possible multilayers of nanoparticles are not covalentlybonded to the substrate. Only the first nanoparticle layer is covalentlybonded. In some embodiments, after each step, the substrate is rinsedwith an organic solvent such as hexane. For example, the hexane canrinse off any nanoparticle weakly attached as a second monolayer or anynumber of additional multilayers. In some cases, sonication can be usedto help remove the excess multilayers.

In other embodiments, the above process, which forms a single monolayerof nanoparticles covalently attached to a substrate, can be repeated asmany times as desired to build up precise layers of nanoparticles, onelayer at a time. In this process, the first monolayer covalently bondedto the substrate is now functionalized—similarly to how the substratehad been functionalized in the first iteration. A second monolayer ofnanoparticles will then covalently bond to the first monolayer, whileany nanoparticle weakly bonded as a possible third monolayer can beeasily removed (e.g., rinsed off). In each subsequent iteration, anothermonolayer of nanoparticles is deposited. The subsequent layers ofnanoparticles can be identical to the nanoparticles in the first layer.Alternatively, different nanoparticles may be added in the subsequentlayers. For example, each subsequent monolayer may be formed with adifferent type or size of nanoparticles, or two types of nanoparticlesmay alternate. By choice of appropriate nanoparticle compositions foreach of the layers, three dimensional materials and metamaterials can befabricated with arbitrary compositions, grading of material properties,and dimensions. Structured nanoparticle assemblies of this type may have“metamaterial” properties such as tunable (and potentially negative)index of refraction, cloaking, wavelength selectable reflection,polarizations, or superlens focusing effects.

In other embodiments, the above process can be stopped before it forms afully closed monolayer of nanoparticles. In some embodiments, the excessnanoparticles multilayers do not have to be removed. In otherembodiments, in the above process does not have to have perfectlyseparated steps. In these embodiments, the modifications from the idealsteps could compromise the quality of the final monolayer, but aslightly imperfect process could be used to shorten fabrication times.In other words, depending on the tolerance to defects of the finalapplication, the process may be modified as a trade off between qualityand ease of fabrication.

In other embodiments, a single, uniform layer of nanoparticles isdeposited on arbitrary surfaces by a combination of gas and liquid phaseatomic layer deposition. According to this method, the substrate surfacecan be functionalized by exposing the substrate to TMA, in the gasphase. This first step may take place, for example, in an atmosphericpressure conveyor belt system or similar systems. Once the substrate isfunctionalized with —CH₃ groups, the substrate is exposed to —OHfunctionalized nanoparticles by spray coating (or other types of coatingsuch as dip coating) in a dry nitrogen environment. Similarly to how wasdescribed above, the nanoparticles will covalently bond to the surfaceof the substrate.

Therefore, the methods described above can be summarized as 1.Functionalization of the nanoparticles; 2. Functionalization of thesubstrate; 3. Covalent bonding of a single monolayer of nanoparticles onthe substrate. The first and second steps may also be performed inreverse order, or simultaneously. As noted above, either one or both ofthe nanoparticle-substrate combo can be bonding without pretreatment.

In other embodiments, the three steps may be modified to be performedwith functionalizing agents in the gas phase, under vacuum, or in theliquid phase, as long as the functionalization of the substrate and thecovalent bonding steps are carried out in an environment substantiallyfree of water or any —OH groups other than the —OH groups on thenanoparticles. Otherwise these additional —OH groups may interfere withthe methods by preferentially bonding the nanoparticles on other, nontarget, surfaces. Additionally, any of the embodiments may be performedin batch or in a conveyor belt-style continuous process. By way ofexample and not of limitation, according to one embodiment, a substrateis placed in a first zone and the substrate is sprayed with TMA, the TMAbeing in the liquid phase. The substrate is then moved to a second zonewith a neat solvent (a stoichiometric solvent) to flush any unreactedTMA from the substrate. The substrate then moves to a third zone whichsprays functionalized nanoparticles onto the substrate surface. Thesubstrate then moves to a fourth zone in which the substrate is sprayedagain with a neat solvent to remove any excess particles.

In other embodiments, the nanoparticles may be functionalized with TMAand the substrate surface is functionalized with alcohol groups. Inother embodiments, TMA can be substituted for any number of potentialreactive precursors used in gas phase atomic vapor deposition such as,but not limited to, chlorides, fluorides, organometallics, or acac(acetylacetonates). In other embodiments, the —OH group may besubstituted with other groups, such as, for example, an amine (—NH₂)group, an ester group, an aldehyde group, a halide, amides, nitriles, orother functional groups known or developed in the art. In otherembodiments, the various functionalized groups disclosed herein can beelongated by attaching a carbon chain between the nanoparticle and itsfunctional group (e.g., the —OH group) and/or adding a carbon chainbetween the substrate and its functional group (e.g., the —CH₃ group).

The methods described herein may be employed together with otherprocesses, or to modify surfaces of existing products. For example,surfaces having covalently-bonded nanoparticles attached thereto can beused as a masking agent for subsequent etching processes. In otherapplications, the covalently bonded nanoparticles can be utilized toallow a solar cell to absorb light at different wavelengths. Thesubstrate of the solar cell can be designed to absorb light at differentwavelengths than the nanoparticles, so the overall energy collected fromthe combined tandem cell can be increased over the single terminal cell.Surfaces modified with nanoparticles can also be used as scatteringcenters on the bottom of existing solar cells to increase the amount oflight absorbed by the cells.

As described above, the present disclosure describes methods tocovalently bond nanoparticles to arbitrary surfaces. The introducednanoparticles can then be leveraged to create novel materials with newlyformed surface topographies. The newly created nanometer scale surfacetopographies change the arbitrary surfaces into valuable new materialsincluding superhydrophilic, superhydrophobic or light-harvestingmaterials. There are numerous known methods for creating functionalizedself-assembled monolayers (SAMs). The present invention uses these SAMsto control valuable surface properties. For example, a substrate may befunctionalized with a SAM. The functionalized nanoparticles can thencovalently bond to the substrate through the SAM.

In some embodiments, the nanoparticles coated on a substrate may be usedto create a mask that partially blocks reactive species from etchingaway at the substrate. The nanoparticles may then be removed, oralternatively remain covalently bonded to the surfaces and therebycreate desired nanometer scale topographies.

In other embodiments, the nanoparticle monolayers can be used todeliberately block a portion of the original surface area, and preventdeposition (limited to the blocked portion of the original area) ofadditional atoms, molecules, compounds, or materials that are beingadded to the surface. In this way, the surface topographies at thenanometer scale can be controlled to create desired surface properties.In other embodiments, functionalized nanoparticles can be covalentlybonded to the SAMs, to allow for desired light absorption or emissionproperties.

FIG. 1 is a schematic illustration of the covalent attachment ofnanoparticles (NP) to a substrate. In FIG. 1, the nanoparticles (105)are functionalized (110) with a group R′, while the surface (120) isfunctionalized (115) with a complementary group R. A covalent bond X isthen formed (125), attaching the nanoparticles to the surface (130). Insome embodiments, instead of a CH₂—CH₂—R chain, simply R can be usedwhere R represents an arbitrary functional group or atom.

Therefore, the SAM on an arbitrary surface is subjected to a reactionwhich covalently bonds the NPs to the SAM. In some embodiments, thenanoparticles may also not be additionally functionalized, if thespecific functional group of the SAM can covalently bond with thespecific material of the nanoparticle. The NP-SAM can be used forfurther manipulations to fabricate surfaces with the desired nanometerscale topographies. Such topographies may render the surfaces, forexample, superhydophilic, superhydrophobic, light emitting, or lightabsorbing.

FIG. 2 illustrates an example of using an NP-SAM complex (205) to modifythe topography of a surface. In this embodiment, the NP-modified SAMsare used as substrates for further manipulations of the underlyingsurface. For example, the NPs may serve as a mask to block the access ofreactive ion species in a chemical etch. Alternatively, the NPs may stopthe growth of newly introduced matter to the surface of the underlyingsubstrate.

In some embodiments, the nanoparticles may be retained on the surface towhich they are already attached to, to obtain a new surface with a newlycreated surface topography (210). In this example, the nanoparticlesremain covalently bonded to the SAM on the substrate. The nanoparticlesprovide access to certain areas of the underlying substrate, andsubsequently a material, e.g. atoms or molecules, may be depositedlimitedly to these accessible areas.

In other embodiments, the nanoparticles may be chemically, or otherwise,removed to provide a surface (215) with a new surface topography that isdevoid of any NPs. In this embodiment, the nanoparticles are used as amask to deposit a material only in specific areas of the substrate. Thecopper catalyzed azide-alkyne cycloaddition reaction (CuAAC) is anexample of the type of reaction that may be used to covalently attachfunctionalized NPs to the appropriately armed SAMs.

FIGS. 3-5 illustrate examples of nanoparticles and substrates withdifferent functionalization. For example, FIG. 3 illustrates an exampleusing the CuAAC reaction. FIG. 3 illustrates an azide-containing SAM(305) that readily undergoes attachment to alkyne functionalized NP(310), with the aid of copper catalysis at room temperature, to give atriazole (315) that attaches the NP to the surface to create aNP-modified SAM substrate.

FIG. 4 also illustrates a surface with an azide monolayer (405), whichcan attach to nanoparticles functionalized (410) withdibenzoazacyclooctyne (DIBAC). The covalent bond (415) is through astrain promoted azide-alkyne click (SPAAC).

FIG. 5 illustrates a substrate with a DIBAC monolayer (505), which canbond to an azide (510) on a nanoparticle. The covalent bond (515) isformed via a strain promoted azide-alkyne click, with a newly formedtriazle ring. In the example of FIG. 5, the substrate and nanoparticlesfunctionalizing agents are reversed, compared to the example of FIG. 4.As understood by the person of ordinary skill in the art, differentfunctionalizing agents can be used. Each functionalizing agent interactswith a complementary agent, but not with other agents of the same group.In other words, the functionalizing agents on the substrate bond to theagents on the nanoparticles, but do not bond to other agents on thesubstrate, nor do the agents on the nanoparticles bond to othernanoparticles. In this way, the covalent bonds are selectively formedbetween the substrate and the nanoparticles, but not betweennanoparticles.

FIG. 6 illustrates a further example of controlled deposition. In thisembodiment, the method is similar to the functionalization and bondingof particles, using trimethylaluminum (TMA) and nanoparticles with —OHfunctional groups. In the example of FIG. 6, a monolayer of aluminumoxide is formed on a surface to bind the particles, as described below.

The high affinity of trimethyl aluminum (605) Al₂(CH₃)₆ for —OHfunctional groups (610) leads to an aggressive reaction to form aluminumoxide and methane. TMA can be introduced, for example, with a TMA pulse.The chemisorption (615) on the surface is self-saturating. The methylligands and the —OH ligands have no affinity for each other, leading tothe self-limited formation of a single monolayer. Subsequently, an “—OHfunctionalized nanoparticle pulse” pulse (623) can be introduced (620).As a consequence, a monolayer, or a sub-monolayer of Al₂O₃ is formed(625), with new —OH functional groups (627) on its surface. In someembodiments, the aluminum oxide layer may be formed without alsointroducing new —OH groups on the surface, depending on whether thealuminum oxide surface needs to be functionally active or not. In someembodiments, commercially-functionalized nanoparticles and a TMAsolution can also be used. For example, carboxylic acid groups onpolyethylene glycol (PEG) encapsulated gold nanoparticles arecommercially available. TMA in hexane solutions are also commerciallyavailable.

In some embodiments, the methods of the present disclosure can beimplemented as a spatially differentiated solution-based ALD. Forexample, the substrate is sprayed with TMA in a solution, in a firstzone of a working area. In a second zone, a neat solvent flushesunreacted TMA. In a third zone, functionalized nanoparticles are sprayedon the substrate. In a fourth zone, a neat solved is sprayed to removeexcess nanoparticles. In some embodiments, dipping steps can be usedinstead of spraying. In some embodiments, solvent mixtures or otherfluids can be used instead of a neat solvent.

For example, FIG. 7 illustrates a working station with multiplefabrication steps. The substrate can be moved across multiple zonesalong a working surface, for example as indicated by arrows (725). Inthe example of FIG. 7, each zone has means for applying a liquid or gasto the substrate. For example, gas bearings or liquid pumps (715) couldbe used to apply fluids in zones (705,717,735). In this example, a first(720) and second (730) precursors can be applied to the substrate in therespective zones. In some embodiments, the precursors are liquids, andliquid flushes can be used in (705,717,735) to flush out any remainingprecursor. For example, this method prevents precursors from mixingbetween each other before being applied to the substrate. Mixingprecursors can cause precipitations instead of deposition on the surfacebeing coated. One of the precursors may comprise particles, as describedabove in the present disclosure. In other embodiments, the precursorsand flushes can be in the gas state. The purpose of zones (705,717,735)is then to vent the precursors. Suitable means to exhaust the fluids canbe placed between the precursor zones and the flushing zones. Forexample, a neat solvent may be used in zones (705,717,735), while theprecursors may be in a liquid solution comprising a solvent. In someembodiments, one of the precursors is a fluid which leaves functionalgroups on the substrate, while the other precursor comprises particleswhich have been functionalized with a functional group complementary tothat on the substrate, prior to spraying the particle suspension on thesubstrate. In some embodiments, the venting or purging steps can becarried out in the same location where the precursors are sprayed.

Several parameters may be adjusted to optimize spray coating, such asthe raster speed at which the substrate is moved between zones (e.g. inFIG. 7), the distance of the spraying nozzles from the substrate,whether the nozzles employ ultrasonics or not, the dispersion ofparticles in the suspension, the pH of the suspension, the use ofsurfactants, and the specific liquid(s), e.g. alcohol, water, or organicsolvents. In some embodiments, a pre-spray sonication step may also beincorporated. Other parameters comprise the flow rate or speed at thefeed tube and nozzle, the orientation of the nozzles, and thetemperature of the substrate. Surfactants can be added to thenanoparticle dispersion as well to prevent or retard agglomeration. Allthese parameters may influence the coating of surfaces, such as theuniformity of the monolayers. The spacing between particles may also becontrolled through the above parameters. For example, having a spacingbetween particles greater than half the particle's radius may beconsidered too large to create a uniform monolayer. In such case, thespray coating would be optimized to give a spacing between particles ofless than half a radius. Spray coating may therefore be advantageous,compared to spin coating, due to the greater control possible duringcoating of the particles on a surface. If the deposition is not uniform,and as the liquid dries, particles could tend to form islands on thesurface, instead of monolayers. In some embodiments, partially closedmonolayers may be useful, and the same fabrication parameters may becontrolled to specify the characteristic length between particles andthe degree of agglomeration.

In some embodiments, the particle size and composition can be controlledto obtain the desired functionality, such as antifogging, visible lighttransmissivity, UV blocking, and etch resistance. In some embodiments,it may be advantageous to have a close-packing arrangement to formmonolayers of particles. However, the particles may aggregate in thesuspension fluid prior to deposition, which may negatively impact theformation of monolayers. For example, a target may be to haveagglomerates of less than 3 particles in the suspension fluid. Forexample, a charge may be established on the particles to ensurecontrolled spreading during spraying of the particles. Surface coatingsmay also be used, either on the particles, the surface to be sprayed, orboth. The surface coatings may, for example, improve adhesion of amonolayer of particles. The surface tension of the substrate may, insome embodiments, be matched to the sprayed fluid. Therefore, thesurface potential can be taken into account during fabrication. Severalfluid parameters can be controlled: dielectric constant (e.g. greaterthan 10), viscosity, volatility, and ability to suspend particles. Forexample, in some embodiments the surface coatings may be important incontrolling surface tension. In some embodiments, it can be advantageousto match the surface tension of the particles to that of the substrate.

Factors leading to spraying of perfect or nearly perfect monolayers ofnanoparticles with no chemical linkages to each other or the substrateare described in the following. The fluid used for dispersion of thenanoparticles is configured to encourage the nanoparticles to remainsuspended. In some embodiments, the fluid can be at higher pH. Forexample, a fluid with pH 10 can be used with alumina particles, toensure the formation of a negatively charged AlO⁻ species on the aluminananoparticle surface. The negative charge on the particles causes themto repel each other, minimizing possible agglomeration. The dispersionfluid, in which the particles are suspended and which is used forspraying or dipping, can contain a surfactant that forms a micellarstructure around the nanoparticles, minimizing agglomeration.

The substrate upon which the particles are to be bonded, and thesuspension fluid, can also be chosen so as to have a good match. Inother words, certain choices for the fluid and the substrate may lead toan increased or decreased capacity to wet the substrate by the fluid.The increased or decreased wetting capacity can improve the formation ofa uniform monolayer of particles depending on the affinity of theparticle for the substrate as compared to the fluid. The substrate mayalso be prepared before the particle deposition, to increase or decreaseits wettability. For example, in the case where water is used, a glasssubstrate can be precleaned with an oxygen plasma to remove any surfaceoil contamination and to create a hydrophilic surface. In someembodiments, instead of a hydrophilic surface, a hydrophobic surface maybe more advantageous, for example, applying hexamethyldisilazane (HMDS)or a fluorocarbon layer to discourage wetting.

The fluid containing the particles can also be configured to evaporaterelatively quickly once it wets the substrate. Otherwise, as the fluidevaporates, the fluid can carry the nanoparticles along the liquid/airinterface as it evaporates, causing the particles to pile up on thesurface unless measures are taken to assure the affinity of thenanoparticles for the substrate. In some embodiments, the evaporationrate can be regulated by controlling the substrate temperature. Forexample, if the fluid is water, the temperature could vary between 5° C.and 150° C. The evaporation rate can also be regulated by controllingthe amount of liquid that is delivered to the surface. Typical flowratescan range from 0.25 ml/min to 2 ml/min. At low temperatures, theparticle motion is controlled by ensuring that there are no surfacetension gradients in the droplets on the surface. At high temperatures,the droplets “flash evaporate” and no surface mobility of thenanoparticles is permitted. It is also possible to apply the liquidcontaining the particles over multiple passes over the same area of thesubstrate, to further regulate the flowrate and evaporation rate.

The nanoparticle concentration and the amount of sonication can alsocontrol the application to the surface of the particles dispersed in thefluid. Typical concentrations are 0.5-5 mg/mL. In some embodiments,sonication can be applied to a rotating canister containing a liquidnanoparticle dispersion, to reduce agglomeration of the particles, forexample for a duration of 1 hour.

When multiple monolayers of particles are deposited in successive steps,different fluids may be used. In other words, the precursor fluid usedto functionalize the substrate may be different from the fluid used tofunctionalize the first deposited monolayer of particles, prior todepositing the second monolayer of particles. In some embodiments, thefluids used have to be substantially inert to the functional groups. Forexample, water would not be an acceptable fluid if the functional groupswere Al—CH₃.

In other embodiments, instead of spray coating, a bath method could beused, where the surface, or part of the surface, is immersed or dippedinto the liquid containing the particles. This method allows coating inbatches. Different applications may favor one application method ratherthan the other. In some embodiments, a catalyst may be used to enablebonding of the particles on surfaces. Chemical or physical means forbonding of the particles on the substrate may be employed, e.g. the useof functional groups on the particles and/or substrate. In theseembodiments, the catalyst may be able to interact with both functionalgroups, the group on the particles and the group on the substrate.

In the following, methods to attach particles by spraying instead ofbonding are also described. The particles can be attached by a varietyof forces, instead of chemical bonds. For example, electrostatic forcesand van der Waals forces. Spraying of nanoparticles to achieve monolayercoverage on a surface requires the concerted engineering effort ofseveral components to the spray.

In some embodiments, the nanoparticles can be dispersed uniformly in afluid that retards the agglomeration of the particles. For an aqueousdispersion, two exemplary ways to prevent or retard agglomeration aredescribed in the following. A first method is to include a surfactantmolecule, for example comprising hydrophilic polyethylene oxide. In amicelluar fashion, the surfactant molecules surround the nanoparticlesin a way that helps to prevent them from crashing out of the dispersionor attaching to other nanoparticles. A second method is to change the pHof the solution, and thereby impart an electrostatic charge to thesurface of the nanoparticles. For example, by adding 0.5 mL of 0.5 MNaOH solution to 250 mL of a commercial aqueous aluminum oxidenanoparticle solution at pH 7, the surface of aluminum oxidenanoparticles becomes as Al(OH)₂ ⁻ as the pH of the dispersion rises to10.5. The effective negative charge on the nanoparticles helps toprevent agglomeration because the particles repel each otherelectrostatically.

In some embodiments, the nanoparticle dispersion can be stirred andsonicated. For example, the nanoparticle dispersions can be stirred andsonicated for approximately 1 hour before use. For example, thesonication power can be set to 100 W, but with a duty cycle of less that50% during that hour in order to avoid raising the temperature of theultrasonic bath too significantly. Temperatures in excess of 40 C canlead to degradation of the surfactant molecules. The stirring andsonication serves two purposes: 1. it homogenizes the mixture ofnanoparticles and surfactant (if present) to ensure that all theparticles have an opportunity to access the surfactant benefit; 2. theultrasonic energy breaks up agglomerated particles to help reduce thechances of delivering an oversized particle to the surface to be coated.

In some embodiments, once the particles suspension is sonicated, it canbe loaded into a syringe pump that is stirred constantly with a magneticstir bar to help prevent settling of the particles. The syringe pumpthen feeds an ultrasonic nozzle with a constant flowrate of thedispersion (e.g. between 0.25 and 5 ml/min) while the nozzle rastersover a part of the surface that is to be coated.

The ideal flowrate of the nanoparticle dispersion is controlled by anumber of factors. For example, by taking the preparation stepsdescribed above, it can be reasonably concluded that the nanoparticlesare not agglomerated when they are delivered to the substrate beingcoated. However, various forces on the surface can cause the particlesto agglomerate and pile up once the particles arrive at the substrate.An important factor is the balance between the rate of evaporation atthe edge of a droplet and the evaporation at its center. If thetemperature of the substrate is too high, there is a difference in thetemperature between the edge of the droplet (in contact with thesubstrate) and the top surface of the droplet (air only contact). Thetemperature difference results in a difference in the surface tensionwhich induces a Marangoni flow within the droplet. The flow leads to theparticles within the droplet being carried to the edge and being piledup as the droplet dries. In some embodiments, to ensure monolayer ornear monolayer coverage, the surface tension difference needs to beminimized, by managing the substrate temperature to be near that of theambient gas. Thus, for water dispersions, the ideal substratetemperature is close to room temperature, while the temperature shouldbe lower for a particularly volatile solvent like isopropyl alcohol(propan-2-ol, IPA).

It can be noted that an alternative approach is also possible wherenanoparticle multilayers can be used to form an effective porous mediathat can also be used as an etch mask. For example, multilayers, 3particles deep, made from an erodible material such as SiO₂ can be usedas a nanotexturing mask for glass. The effective media method leavesholes and packing defects which ultimately translate into nanotextureswhen the media is eroded. This can make the overall texturing processless sensitive to forming a perfect monolayer. Degree of porosity can becontrolled by selecting larger or smaller nanoparticles to form thelayer. An exemplary case is 30 nm SiO₂ nanoparticles multilayers, 6layers deep, on glass etched with a fluorocarbon-based plasma. Thesubstrate temperature in this case can be higher (e.g. 75° C. or above)with less penalty than the monolayer deposition method. In addition,mixtures of erodible nanoparticles such as SiO₂ and non-erodiblenanoparticles such as Al₂O₃ can be used in varying ratios. The erodiblenanoparticles help to better distribute the Al₂O₃ on the surface,governing the ultimate surface textures.

To ease the formation of monolayers, it can be useful to create aninherent affinity between the nanoparticles and the surface that is tobe coated. The paragraphs below describe two methods that result inpreferentially forming chemical bonds between the nanoparticle and thesubstrate surface (click-type organic chemistry and ALD-type inorganicchemistry). However, it can be noted that there are other ways that cancreate a preferential physical only interaction.

Some exemplary examples of physical (not chemical bond) attractionsinclude: 1. creating a charge on the surface by creating a positivecharge on the substrate (by ion bombardment to give one, non-limiting,example) and using a pH greater than 7 to cause the nanoparticles tohave a negative surface charge. 2. Creating a hydrophilic interactionwhere the surface and/or the particles are pretreated with a film or anO₂ plasma to generate —OH groups, and the hydrophilicity of the surfaceattracts the first layer particles.

The advantages of creating an attractive force (either chemically orphysically) is making spray processes less sensitive to sprayparameters, and making dipping processes viable without resorting toLangmuir-Blodgett techniques. Both of these features make a nanoparticleattachment process as described in the present disclosure more robustand easier to integrate into commercial products.

In some embodiments, ALD methods described above can be used, forexample, to fabricate tandem solar cells or cells to be used in tandemwith other cells. For example, the surface of silicon solar cells can bemodified to increase efficiency, by coating them with nanoparticles. Forexample, the nanoparticles can increase the efficiency of absorption inthe UV (ultraviolet) and visible spectrum of silicon cells. The combinedefficiency can be increased to 25% or greater. The nanoparticles canalso act as scattering centers on the bottom of existing cells toincrease the amount of light absorbed by the cells, as the light isscattered towards into the cells.

In other applications, the surfaces modified with nanoparticles can beused in catalysis or battery applications. The methods described hereinallow selective 3D loading of nanoparticles on the surface. In otherwords, the surface can be controlled at the nanoscale level. It shouldbe noted that the surface, in this case, refers to all exposed surfacesthat can be reached by the nanoparticles. For example, some materialslike zeolites, polymers, or metal-organic frameworks (MOF) have aninternal and external surface area. The methods of the presentdisclosure can refer to all of such surfaces (the entire 3D topology).In some applications, the nanoparticles on the surface can also be usedas absorbers for infrared detectors.

The chemical methods described herein (both organic and inorganic)present a significant improvement over DNA-based methods since the bondbetween the nanoparticles and the substrate is a covalent bond. Thesurface links to the nanoparticles have improved temperature andchemical stability, and can be considered permanent. The methodsdescribed herein also allow the fabrication of hierarchical surfaces,since the nanoparticles can be deposited in several monolayers with adifferent topography, forming 3D structures that influence the physicaland chemical properties of the substrate.

The methods described herein can also be effectively used to apply asingle layer of nanoparticles onto curved or other non-uniform surfaces.Multiple monolayers of nanoparticles may also be deposited on curvedsurfaces, by attaching the nanoparticles to the surface by directbonding, through chemical functional groups on its surface which willform a strong, chemical bond with the functional groups on thenanoparticle. In the absence of such chemical bond, prior art techniquesrequired activating the materials' surface before coupling thenanoparticles. Surface activation is a process of generating, orproducing reactive chemical functional groups typically using harshchemical or physical techniques. Therefore, the methods described hereinare advantageous as they can be applied to a variety of surfaces whichwould be negatively affected by harsh chemical or physical techniques.

As described above, surfaces can be modified to provide a texturedsurface that can be patterned or otherwise tailored for a desiredapplication. In some embodiments, one or more surface structures and/orone or more layers may be applied to the substrate surface in order tomodify or alter one or more of the substrate surface's physicalproperties including, but not limited to, wettability, propensity topromote or inhibit adhesion, conductivity, surface charge, propensity topromote or inhibit condensation, evaporation, corrosion, sublimation,reflectivity, emissivity, light filtering (high, low, or bandpass),light absorption (including polarization), and fluid absorption.

As described in the present disclosure, the modified surfaces aredesigned to provide a combination of modified physical properties to thesubstrate. In some embodiments, the modified physical properties can beinherent to the underlying material or substrate, because the modifiedphysical property is not the result of a coating but is inherent of thematerial. In other words, in some embodiments, the structure itself hasat least one of the desired properties. For example, nanoparticles arenot needed to obtain UV blocking and antifrosting if the structures havedimensions of 200 nm or less, and have hierarchical nanotextures (nanoon micro, or nano on nano, e.g. pillars with rough edges). Nanoparticlescan be deposited on the UV blocking structure to also add IR blocking.That structure would be inherently UV blocking and anti-frost, but notinherently IR blocking. This fact provides increased durability as wellas consistency of the physical properties over time. The enhanceddurability provides a greater resistance to physical damage due toabrasion and delamination, which may otherwise occur with coatedsurfaces. In the following, several exemplary applications andembodiments are described. Although some applications are described withexamples, these examples are not meant to be limiting. For example, thefollowing example is described as relevant to aircraft, however it mayalso be applied to naval vehicles or other fields.

Anti-Frost in Combination with Radio Wave Absorption.

In this embodiment, one or more external surfaces of an airplane,helicopter, drone, or other flying aircraft could be modified to inhibitthe formation of ice (by being hydrophobic) and be made to absorb radiowaves to prevent detection via radar (e.g. stealth). In thisapplication, the external surfaces can be modified after theirfabrication, or the surface-enhancing method can be applied duringfabrication of the relevant structural components. For example, themethods as described in the present disclosure may be applied to a wingmanufactured by an aeronautical company, or the methods may beintegrated in the manufacturing of the wing.

The structures comprising external surfaces (external to the aircraft)could also be modified to improve the aerodynamic or hydrodynamicperformance of the craft. For example, the surface of the aircraft canbe made from a composite that incorporates a base layer of a materialcapable of absorbing radio waves. A hydrophobic surface treatment canthen be applied by texturing the surface of the composite panel. Forexample, a composite containing iron nanoparticles can be textured withmicro- or nano-sized features (e.g., spikes or holes) to create theanti-frost and radio wave absorbing effect. In various embodiments,different portions of the composite panel may be provided with moreradio wave absorption properties and other portions could have greaterhydrophobic properties. In another embodiment, the surface of theaircraft can have a hierarchical structure where the characteristiclength of the larger structures is designed to absorb radio waves andthe length of the smaller structures is designed to be hydrophobic torepel water and ice. An example of the hierarchical dimensions could bemillimeter-scale larger features combined with micro- or nano-scalefeatures.

Anti-Frost/Fog in Combination with UV and IR Absorption.

In this embodiment, a car windshield could be fabricated to preventfrost formation on its external surface, as well as to prevent formationof condensation on its internal surface. The windshield may also be madeto absorb or scatter UV light from the sun, as well as absorb IR light(e.g. to regulate the temperature within the car in hot weather). Forexample, a multifunctional surface could comprise a glass windshieldtextured on the inside or outside to have some structures less than 400nm in size, and some structures with a size greater than 100 nm. Thelarger structures would inhibit frost formation while still allowingvisible light to pass; the smaller structures would promote UVscattering and/or absorption. This embodiment could also have a coatingof semiconductor nanoparticles that have a bandgap to enable IRabsorption, while being small enough to avoid scattering visible light.The coating might be applied to a window and then textured to enableantifogging properties while remaining transparent to visible light andopaque to UV light. The coating of nanoparticles can also be appliedafterwards.

Anti-Fogging in Combination with UV Absorption, Polarization, Off-AxisLight Rejection, and Anti-Reflection in any Combination.

In this embodiment, a lens (for a goggle, glasses, mask, or othereyewear) is fabricated to have specific nanotextures. The size of thenanotexture enables UV absorption and anti-fogging, while the heightenables anti-reflection of visible light, and the shape enablespolarization. For example, using non-spherical nanoparticles, such aselliptical nanoparticles, would enable polarization control. To achievethese effects the following conditions need to be achieved: 1) Thestructures must be large enough to scatter the incoming UV light. Forexample, the structure could have elements each having a width of100-300 nm. 2) To achieve antifogging, the structures should be spacedat a distance no greater than the characteristic size of a water dropletat the intended humidity and surface temperature operating conditionsfor the structures. For example, the spacing may be less than 10micrometers. 3) To achieve anti-reflection, the nanostructures shouldhave a vertical height such that the effective medium formed by the airand the nanostructures is tailored to ensure an anti-reflectioncondition. 4) To achieve polarization control and off-axis lightrejection, the nanostructures should be anisotropic in one or more of anumber of dimensions. For example, the elements forming the structurecan be elongated with aspect ratios greater than one, e.g. 1.5. Theaspect ratio, for example, could be considered as the ratio between thelongitudinal axis and the lateral axis of an elongated shape. Thenanostructures may also be tilted so that the path difference for thelight in one direction is different than for the other direction. Thenanostructures can also be tilted such that the characteristic dimensionof the structure (e.g. the size of one of the constituting elements,such as a nanopillar width or height) in the direction of light travelis less than the scattering size (e.g. 400 nm for visible light), andgreater than the scattering size (e.g. greater than 400 nm) in adifferent direction.

Anti-Fogging/Frost in Combination with Broadband Anti-Reflection andBroadband Absorption and Conductivity.

In this embodiment, a series of structures and layers is added to asolar cell to increase its efficiency (i.e., the ability to convertsunlight into electricity). One or more layers of nanoparticles with avariety of bandgaps can be added to the top surface of a solar cell toincrease the range of light absorption. This allows the solar cell tocapture a greater percentage of light from the sun because a broaderrange of wavelengths may be absorbed by the solar cell. To facilitatethe collection of the electrons generated by light absorption in theselayers, the links between nanoparticles or between the nanoparticles andthe substrate (or the surrounding media) can be made conductive toenable energy to be collected by the solar cell substrate. Layers canalso be added to the top of the nanoparticle absorber layers, to inhibitfrost formation or dust collection on the surface of the solar cell, andtherefore improve collection efficiency. In addition, one or more layerscan be designed to emit radiation in the mid-long wavelength range ofthe infrared band (around 8 micrometers, e.g. in the 7.5-8.5 micrometersrange) where there is an atmospheric wavelength window to space. Thisemission can be used to cool the solar cell to improve efficiency, evenin bright sunlight, due to the emission of light into the cold, darknessof space. In other words, the modified layers added to the solar cellscan be designed to emit in the infrared band to cool off the solar cell,by radiating heat into space. In other embodiments, the bottom of thesolar cell can be tailored to promote scattering of the sunlight backtowards the absorbing regions of the solar cell. In some embodiments,the bottom of the solar cell can be modified to include upconvertingnanoparticles to convert longer wavelength photons to shorter wavelengthphotons to increase their collection. The energy from these shorterwavelength photons can be collected in a location near to theirconversion, or can be reflected back into the main portion of the cellfor absorption in a more ideal location.

In the fabrication of a single monolayer of nanoparticles, multiplemonolayers of nanoparticles, or more complex structures modifying theproperties of a surface, several parameters can be controlled to achievethe desired characteristics. For example, the nanoparticle size andcomposition can be controlled to achieve the desired functionality, suchas anti-fogging, visible light transmission, UV blocking, and etchresistance. The nanoparticles aggregation is also a parameter that canbe controlled. For example, during spraying the electrostatic charge onthe particles or the ultrasonic energy applied to the spraying nozzlecan affect the aggregation between nanoparticles and cause unevendeposition. Controlling the electrostatic and ultrasonic energy inputcharge can allow controlled spreading of the nanoparticles onto thesubstrate. For example, one target could be to have less than 3nanoparticles agglomerated. In some embodiments, surface coatings couldbe sprayed on the substrate or onto the nanoparticles prior to thenanoparticles being applied. The fluid parameters can also be controlledto optimize spraying. For example, the viscosity, volatility anddielectric constant, as well as the ability of the liquid to suspendparticles, are characteristic to be considered in the choice of theliquid. For example, the dielectric constant of the liquid, in someembodiments, is higher than 10. Another parameter to be considered isthe surface tension of the surface to be sprayed. In some embodiments,the surface tension is matched to the sprayed fluid. The surfacepotential of the substrate may also be considered.

FIG. 8 illustrates an exemplary surface that is substantiallytransparent to visible light while substantially blocking UV light. UVlight has shorter wavelengths compared to visible light. The samesurface, having a nanostructured surface, will appear differently toincident UV light compared to incident visible light. In this example,the surface (805) comprises a non-uniform jagged nanostructure, whichcould be described as rough when viewed in a magnified way (806). The UVlight will undergo significant scattering, and the transmitted light(815) will have an overall total intensity that is lower than the lightthat is reflected (810). For the case of visible light (821), however,the same structure will appear to have a smaller size, or roughness,relatively to the case for UV light. In other words, the nanostructureswill appear small, for the case of visible light. The decreasedroughness (relative to the wavelength of the incident light), will causedecreased scattering, and the total transmitted intensity of light (820)will be higher than the intensity of light reflected (825). Due to thedifference in wavelength, the surface will appear rough to UV light andsmooth to visible light, causing a difference in scattering.

FIG. 9 illustrates an exemplary surface for UV blocking and visiblelight transmission, as described above with regard to FIG. 8. In thisexample, the surface has comprises a non-uniform jagged nanostructurewith dimensions between 100 and 200 nm. This structure could be usedalso for antifrost applications. While a structure with dimensions inthe 40 nm range could be used for antifrost applications while beingtransparent to visible light, increasing the dimensions to 100-200 nmalso allows UV blocking. In fact, a structure with dimensions in the 40nm range allows antifogging if the size of the droplets is greater than40 nm, as in this case the droplets are discouraged from forming orattaching to the surface. If the structure has dimensions in the 100-200nm range, the size of the droplets is still larger, therefore theantifogging characteristic is preserved, while the added functionalityof UV blocking is added.

In some embodiments, surfaces can be patterned to define textured andnon-textured regions that, in one embodiment, would result in foggingand antifogging regions. For example, the nanoparticles can be sprayedin a controlled way. The spraying pattern can be regulated to have theshape of a fine-tipped pen. The cross-section of the spray pattern wouldbe the same as the smallest feature of a region to be patterned. Forexample, if the regions having different properties (e.g. fogging vsantifogging) are x micrometers wide, the cross-section of the sprayednanoparticle suspension would also be x micrometers wide. Due to thespatial selectivity of the spray, only the regions that are coated willhave antifogging properties. In some embodiments, the spray coater canachieve about 1 micron spot size. In some embodiments, the spray can beachieved with an inkjet.

In other embodiments, a shadow mask can be used to block certain regionsof a surface from being sprayed on. After spraying and removal of theshadow mask, the blocked regions of the surface, if placed in thecorresponding environmental conditions, will fog, while the unblockedregions will not fog. A possible application of the above methods is tomanufacture logos on different surfaces. For example, an exemplaryapplication would be hotel bathroom mirrors that do not fog, except fora small region of the mirror which will fog to reveal the hotel brandlogo. In other examples, other types of text could be designed onsurfaces.

In some embodiments, a logo can be fabricated by creating a hole in asheet of material, such as a sheet of metal. The hole can be shaped toform a text, or an image, for example a brand logo. Subsequently, ananoparticle mask and etching can be applied to another substratethrough the sheet of metal by spray coating. If the sheet of metal isused to fabricate a mirror, the nanoparticles will coat the mirror inthe shape of the brand logo. This limited surface will have antifoggingproperties, unlike the remaining portion of the surface which will fogif the humidity is high enough. The reverse case, where only the logo ordesired pattern fogs and the rest does not, is also an option dependingon the shape of the hole(s) in the metal and subsequent processingsteps.

In some embodiments, the structures fabricated according to the presentdisclosure are wear-tolerant structures that expose new nanotextures asthe material wears down. The structures are designed and fabricated tokeep their functionality intact once the external layers (in contactwith the environment) are gradually worn down, progressively exposinginner layers. For example, the structures can comprise multiple layers(e.g. tall structures), but have hierarchy so that, as the top portionof the structure is removed, the middle portion and the base portion ofthe structure continue to have antifogging textures available.

In some embodiments, the fabrication of hierarchical surfaces allows therealization of surfaces with different properties, such as a surfacehaving both UV protection and anti-fogging capabilities. For example,different layers each having a different number of particles may beused, or each having differently sized particles. In these embodiments,the size of the structure allows visible light to be transmitted throughthe surface, while blocking UV light. The particles could be positionedclose enough to control hydrophobicity of the structure, or allowanti-fogging effects. In some embodiments, instead of sphericalparticles, elongated particles may be used for polarization control. Forexample, rods or ellipsoids may be used.

In some embodiments, anti-reflection can be achieved by increasing theaspect ratio of the structure. For example, tall structures can be usedfor anti-reflection. The maximum width of each element in the structurewill control the transparency to specific wavelengths. For example,referring to FIG. 9, each of the peaks (905) will have a height andmaximum width. The peaks may represent a jagged structure, or, in otherembodiments, the structure may be formed by nanopillars, micropillars,or by structured layers of particles. For example, particles could bearranged to form pillars. The height of these peaks can control thereflectivity of the surface. Therefore, having a structure with higherpeaks can give anti-reflective properties to the surface. The width ofthe peaks (e.g. the width of the nanopillars) can control thetransparency to light at certain wavelengths. The geometrical dimensionwhich controls the transmission of the light is the maximum width of theelements forming the structure, in the direction of the incident light.For example, if the maximum width is 100-200 nm, UV light can beeffectively blocked, while visible light is transmitted.

In some embodiments, a surface can be modified to have antireflective orhighly reflective properties according to the concepts described in thefollowing.

In some embodiments, a surface is textured in a way so as to increase ordecrease the reflectivity of light incident upon the surface as comparedto an untextured surface. In these examples, the characteristic lateraldimensions of the surface texture are smaller than the wavelength of thelight. The surface texture may comprise a number of elements, forexample nanoparticles, or nanoparticle groups, nanopillars, nanorods,irregular jagged peaks, uniform triangular structures, or other types ofstructures. The lateral directions of the elements that make up theoverall surface texture can be defined as in the plane of the surface,for example as the width of each nanopillar, or the average width of thenanopillars if the pillars are not uniform in width.

The depth of the texture normal to the surface can be designed to modifythe refractive index of the surface. For example, the height of pillarswill control the refractive index of the surface texture. The depth ofthe structure on the surface causes constructive or destructiveinterference of the light at a specified wavelength, or range ofwavelengths. As known to the person of ordinary skill in the art,electromagnetic radiation will undergo reflection and transmission ateach interface between materials having a different index of refraction.In the right conditions, such as in a structure having dimensions of theorder of nanometers or micrometers, the electromagnetic radiation willundergo interference, which can be constructive or destructive. Thiseffect can be controlled by choosing the thickness of each layeraccordingly, depending on whether constructive or destructiveinterference is desired at that specific wavelength. In embodimentswhere the textured surface is manufactured using an absorbing material,the modification of surface reflectivity may also increase or decreasethe absorptivity at a specified wavelength or range of wavelengths ofincident light, as compared to an untextured surface. In otherembodiments where the textured surface is manufactured using atransparent material, the modification of the surface reflectivity mayincrease or decrease the transmissivity at a specific wavelength orrange of wavelengths of incident light, as compared to an untexturedsurface.

The polarization properties of a surface can also be controlled bydesigning the surface structure. In some embodiments, a surface istextured in a such a way that the reflection, transmission, orabsorption of light incident on the surface is dependent on thepolarization of the light incident upon the surface. For example, lightreflected from the environment may have a preferred polarization. Asurface can respond to this polarization to decrease reflection; forexample, this effect can be used in sunglasses. In these embodiments,the characteristic lateral dimensions of the surface texture are smallerthan the wavelength of incident light. In these embodiments, the lateraldirections are defined as those in the plane of the surface, e.g. thelength of beams formed with a longitudinal axis parallel to the surface.The surface, in some embodiments, can be manufactured using a materialwith dichroic or birefringent properties. In some embodiments, thesurface can be manufactured using a material with dichroic orbirefringent properties that arise from the modification of a singlematerial or the combination of materials. In some embodiments, thesurface can be manufactured using plastic synthesized from iodine-dopedpolyvinyl alcohol. In other embodiments, the surface can be manufacturedusing a material with dichroic or birefringent properties due to theinherent atomic structure of the material.

In some embodiments, a surface can be textured in a such a way that theabsorption of light incident on the surface is dependent on theorientation of the electric field of the light radiation. The surfacecan therefore acquire polarization effects. In these embodiments, thesurface can be manufactured using a material with an absorbing layer offinite thickness on top of a material with dissimilar opticalproperties. In these embodiments the surface texture extends to a depthnormal to the surface without discontinuities in the absorbing layer. Inthese embodiments the structure is asymmetric in the direction parallelto the electric field of the incident light (incident electromagneticradiation), relative to the direction perpendicular to the electricfield (in the plane of the surface upon which the electromagneticradiation is irradiated). Due to the asymmetry, radiation with anelectric field parallel to the direction where the elements of thestructure are elongated is preferentially absorbed, compared toradiation with an electric field perpendicular to the elongated axis.The overall effect is that the structure has polarizing properties. Theelongated structure can be realized in different ways. For example,elongated ellipsoidal particles or nanorods could be used, if thelongitudinal axis of each particle or rod is aligned in a common,parallel direction.

It is possible to understand the polarization effect by considering anarray of conductive wires spaced apart and parallel to each other, asillustrated in FIG. 25. FIG. 25 illustrates exemplary wires with a width(for wires with a rectangular cross section) or diameter (for wires witha circular cross section) of 50 nm, and spacing of 250 nm, for anincident radiation at 500 nm. The spacing is therefore roughlycomparable to (or slightly smaller than) the incident wavelength, whilethe width is much smaller than the wavelength. With an incident wavehaving the electric field oriented in plane as in (2015) (in the planeof the figure), and the corresponding magnetic field as (2510), theradiation will be preferentially absorbed with the electric field indirection (2015), parallel to the longitudinal axis of the wires (2505),relative to radiation with an electric field in direction (2510).Therefore, a surface comprising an array of conductive wires ispolarization-sensitive.

A similar structure could be realized by spray coating (or dipping)elongated particles or nanorods on a surface, or by etching beams on asurface. For example, orientation during spray coating or dipping couldbe carried out under an applied electric, magnetic or both electric andmagnetic field. If the elongated particles are electrically polarized,or are sensitive to the magnetic field, the particles can align in aparallel direction during deposition. For example, the presentdisclosure described, above, how using inorganic precursors allowsstable bonding of particles on a surface. If the particles areelongated, the coating carried out under a bias field could allow thecreation of polarization-sensitive surfaces, alone or in combinationwith other surface modifications such as discussed above (UV blocking,antifogging, etc).

In some embodiments, to create polarization-sensitive surfaces, thelateral spacing between discontinuities is smaller in the directionperpendicular to the electric field compared with the spacing betweendiscontinuities in the direction parallel to the electric field of theincident electromagnetic wave. In some embodiments, the textured surfaceis created by depositing particles upon the untextured absorbing layer.In these examples, the particles have a characteristic axis. Along thischaracteristic axis, the particles are at least twice as long ascompared to the dimensions of the particle along the axes perpendicularto the characteristic axis.

The particles can be preferentially aligned in a specific lateraldirection, and in some embodiments the particles are used as a mask totransfer a pattern into the underlying surface. The resulting texturedsurface results in absorption of light incident on the surface that isdependent on the polarization of the light. In some embodiments, theelongated particles possess an electric or magnetic polarity such thatthe particles can be aligned upon the untextured surface using anexternally applied electric or magnetic field. In some otherembodiments, the elongated particles possess an electric or magneticpolarity such that the particles can be aligned upon the untexturedsurface through electromagnetic interactions with one another. In otherembodiments, the elongated particles are attached to other moleculessuch that the particles can be arranged upon the untextured surfacethrough chemical reactions between the molecules. In some embodiments,the elongated particles are attached to deoxyribonucleic acid (DNA)molecules such that the particles can be arranged upon the untexturedsurface through DNA self-assembly.

In other embodiments, the elongated particles are applied to theuntextured surface using a process that imparts velocity to theparticles along a specific lateral direction, thereby causing theparticles to align in such a way that their longest dimension isoriented in the same direction. In other embodiments, the elongatedparticles are applied to the untextured surface, which is subsequentlystretched in a specific lateral direction, thereby causing the particlesto align such that their longest dimension is oriented in the samedirection. In some embodiments, the elongated particles are arranged onthe untextured surface through chemical or electromagnetic interactionswith features already patterned on the surface. In some embodiments,elongated particles will have a longitudinal length comparable to theincident wavelength, and a width (in-plane) smaller than the incidentwavelength. FIG. 25 illustrates an example of elongated particles (2520)aligned along their polarity axis to form a structure functionallyequivalent to the wires (2505).

In some embodiments, a surface can be textured in a way so as to limitthe angles over which light is transmitted or reflected relative to thesurface. For example, such surfaces can be used as privacy screens tolimit viewing of a computer screen from certain angles. The depth of thetexture normal to the surface, in these embodiments, is greater than thewavelength of the light. For example, the height of nanopillars ornanobeams, if greater than the wavelength of incident light, will limitreflection at certain angles. For example, reflection at angles greaterthan a certain value will be limited, and therefore only a viewersubstantially facing the front of a screen will be able to discerndetails on the screen. In some embodiments, the voids within thetextured region (e.g. the empty space between nanopillars) are partiallyor completely infilled with a material of dissimilar refractive index.In this way, the textured region is mechanically strengthened by theinfilled material. In some embodiments, the textured region is infilledwith a solution-based polymer that is subsequently cured to form a solidmatrix. Structures having high aspect ratio pillars can be understood towork as an array of vertical fiber optic. Internal reflection of fiberoptic limits their emission to a cone, when exiting the fiber optic.Similarly, it can be understood that light from a specific angle will beable to enter the top end of the pillars. In some embodiments, lightexiting the structure through the pillars can act in a similar way as anarray of parallel fiber optics. Either way, the reflection ortransmission of light at specific angles can be controlled by design. Insome embodiments, pillars with a high aspect ratio can control thereflectivity of a surface. Additional properties can be controlled,according to the principles described in the present disclosure. Forexample, if the width of each pillar is about 100-200 nm, the structurecan block UV light while being transparent to visible light.

In the following, several examples of modifications of surfaceproperties will be illustrated with reference to FIGS. 26-30. Forexample, FIG. 26 illustrates an exemplary monolayer of microspheres(2605) deposited on a surface with the any of the methods describedabove with reference to FIGS. 1-7. FIG. 26 also illustrates an exemplarymethod using nanoparticles or microspheres as an etching mask. Theparticles (2615) can be deposited in a desired pattern, for example inparallel rows or dashed parallel lines. An etching step is subsequentlyundertaken, by an etchant that can etch the substrate without etchingthe particles (or at least with a significant difference in etching ratefor the two materials). As a result, the regions of the substrate notcovered by the particles are etched (2610), forming, for example,parallel beams (for parallel rows of particles) or nanopillars (fordashed parallel lines of particles) on the substrate. The above etchingprocess can therefore be considered anisotropic. Subsequently, theparticles can be removed, or left on the surface, depending on theapplication. For example, FIG. 26 shows single particles on each beam,however a number of regions with one or more monolayers of particlescould also be deposited instead. Therefore, the surface not attacked bythe etchant could have surface properties modified by the particle'sstructure, as described above in the present disclosure. The etchedsurface may also be subsequently processed, for example by addingadditional nanoparticle structures to further modify the physical orchemical properties of the substrate.

For example, additional particles may be deposited on the surface of thebeams or pillars, within the spacing, as illustrated in FIG. 28. In someembodiments, a spacing can be left between particles deposited laterallyon the beams or pillars. For example, the spacing could be larger thantwice the diameter of a particle, but could also be smaller or larger.These particles can be used to modify the surface properties. In someembodiments, the particles can also be used as an etchant mask as well,to create additional structures on the sides of the pillars, such asillustrated, for example, in FIG. 27, (2705). In some embodiments,several properties of the surface can be controlled at once. Forexample, the height of the beams or pillars in FIG. 27, as well as thespacing, could control the transparency to specific wavelengths, thepolarization sensitivity, and also the reflectivity at specific angles.For example, high aspect ratio structures could control thereflectivity, while the spacing between elements of the structure, aswell as the height and width of the elements of the structure, couldcontrol polarization sensitivity and transparency at specificwavelengths (e.g. UV blocking).

FIG. 27 illustrates an exemplary groove or pyramid (2710) which could beused for radar reflection, for example to fabricate radar-stealthsurfaces. For example, the grooves could have lateral or depthdimensions of the order of wavelengths used in radars. An array ofgrooves could control radar reflectivity of a surface. The grooves couldalso be further modified, with the methods described above in thepresent disclosure, to add additional properties such as, for example,antifogging or antifrosting. For example, FIG. 28 illustrates a grooveor pyramid with an additional structure added at a smaller scale. Forexample, beams or pillars (2810) could be etched by using a particlemask as in FIG. 26 (2610) or FIG. 27 (2705). In some embodiments, thegrooves or pyramids can have dimensions in the millimeter range, whilethe additional textures as (2810) could be in the nanometer range. Apossible application could be to fabricate surfaces (e.g. airplanewings) resistant to frost and with lower radar signatures. In someembodiments, the gap between particles deposited in the recesses of thestructure in FIG. 28 is substantially greater than double the diameterof the particles. In FIG. 27, the shape could represent a pyramid.

Referring to FIGS. 27 and 28, an inherently antifrost structuralmaterial that also has low visibility to radar can be realized, forexample, if the roughness of the surface in (2710) or (2810) is 50 nm to1 micrometer. In some embodiments, the surface may comprise an array ofsmall structures such as (2705). The lateral dimension of each invertedpyramid (2710) or grooves can be of the order of one millimeter.

FIGS. 29-30 illustrate an exemplary array of structures. For example, anarray of nanopillars (2905) or rectangular cross-section structuresviewed from above in FIG. 29 can be used to control surface properties.FIG. 30 illustrates a side view of structures on a surface, with thestructures having sloped side surfaces (3005). In some embodiments,additional materials may be present on top (3010). The structures ofFIG. 30 can be fabricated, for example, by masking with particles asillustrated in FIG. 26. Particles may also be coated on the structuresof FIG. 30 to further modify the properties of the surface.

In FIG. 30, it is possible to distinguish three different zones: a firstzone (3015) with a substrate having a refractive index n₁, a second zone(e.g. air) having a refractive index n₂ (3025) and a third zone with athird (effective) refractive index n₁(z) (3020). The third zone cancomprise regions having both the first and second refractive index. Theeffective refractive index of the third zone, for the case where themedium of the second zone is present between spacings of elements of thethird zone (e.g. air between beams) can be calculated as the geometricaverage of the refractive indexes of the first and second zones, asunderstood by the person of ordinary skill in the art. The structuresthat modify the properties of a surface with regard to incident light(e.g. transparency) can be fabricated in the third zone. In someembodiments, the thickness, depth or height of the third zone is equalto ¼ of the ratio between the incident wavelength and the effectiverefractive index of the third zone. The height, spacing and thickness ofthe elements in FIG. 30 can be controlled to regulate how the surfaceresponds to electromagnetic waves. For example, the spacing betweenelements, if less than one half of the incident wavelength, can blockthe incident wavelength.

For example, a structure as in FIG. 30 can block UV light and betransparent to visible light if the spacing between elements is about250 nm. This spacing will block UV light, as UV light has a wavelengthcomparable to the spacing (e.g. 40-400 nm), while visible light at awavelength of 500 nm or greater will be transmitted through the surface.The structure of FIG. 30, if designed to block UV and be transparent tovisible light, could additionally be modified to have other propertiesas well, such as antifogging or antireflection. One way in which thethickness of the structure influences the transparency of incidentelectromagnetic waves is due to the reflections at each boundary—e.g.the boundary between the material and air. Reflections from differentboundaries can interfere in a constructive or destructive way. If thethird zone comprising a structure is considered as having an effective(e.g. geometric average) refractive index and thickness, constructive ordestructive interference at boundaries between the first and third zonesand between the third and second zones can be considered to controltransparency of the structure to incident electromagnetic waves.

With reference to FIG. 26, a structure could comprise InGaAs particles(2615) of a specific diameter, to absorb infrared light. The diameter ofthe particles would control the width of the elements in the structure.The depth (height) of the structure could control the reflectionproperties of the surface. The spacing between elements could controlthe antifogging properties of the surface. In some embodiments, theheight of the structure could be about 400 nm.

FIG. 36 illustrates an exemplary embodiment of a multifunctionalstructure (3605). In this example, the structure comprises a repeatingarray of pillars, each pillar having recesses, similarly to FIG. 27. Insome embodiments, the recesses may be fabricated by differential etchingusing particles as an etching mask. In this example, the resultingstructure is covered by a monolayer of particles. A lateral dimension(3610) of the pillars can be indicated as x, the height (3615) of thepillars can be indicated by y, and the other lateral dimension (3620)can be indicated as z. These parameters can be varied to controldifferent properties of the surface. Additionally, other parameters suchas material choice or spacing between pillars may also be specified. Forexample, if x is between 50 nm and 250 nm, it will enable UV blocking;if y is about one quarter of the incident wavelength, e.g. y=150 nm, itwill enable anti-reflection; if z is greater than x, for example if z isat least three times x, the surface will be polarizing. Additionally, ifthe particles forming the monolayer have a diameter less than 200 nm andare made of an absorbing material, the particles can provide IRabsorption. For example, the particles may be made of Si, GaAs, orsimilar absorbing materials. If x and z are less than 400 nm, thesurface will be transparent to visible light. If y is greater than x,for example greater by at least 5 times (or 3 times), the surface willprovide angle selectivity (e.g. for privacy screen protectors). In someembodiments, x and z can be substantially equal in value.

In view of the above, in the example of FIG. 36, a UV blocking,antireflection, IR absorbing surface transparent to visible light couldbe realized with x=z=200 nm, y=150 nm, and with Si particles having adiameter of 50 nm.

FIG. 31 illustrates exemplary elements that could be included in astructure, as described in U.S. Pat. No. 8,691,104, the disclosure ofwhich is incorporated herein by reference in its entirety. In someembodiments, controlling the hydrophobicity of a surface, in addition toother properties as described above, can be carried out as described inthe following, and as described in U.S. Pat. No. 8,691,104. In someembodiments, the structures projected from a surface as in FIG. 31 canalso be realized in a negative space version. For example, in FIG. 31,it is also possible to read the shapes as grooves or recesses in amaterial, if inverting the orientation of the shapes by 180° degrees inthe plane of the figure. These shapes can be considered as the reentrantor inverted version of the shapes considered as projecting from asurface. Structures having these shapes can be additively orsubtractively combined in any weighting to produce other desired shapes.

For example, for a fixed macroscopic surface area, a microscopic surfacearea can vary and can be controlled by nanotexturing the surface, forexample, by providing nanostructures on the surface, thus providing anincreased microscopic surface area. In particular, according to thepresent disclosure, a higher microscopic surface area can be achieved bya higher number of nanostructures per unit area thus obtaining a highermicroscopic surface area over a fixed macroscopic surface area. The sizeof the textures that affect the properties of a liquid droplet can alsobe micron-sized and therefore the size of the nanotextures referred toin this disclosure should not be considered to be limited to less than1000 nm in size.

In particular, in some embodiments by controlling the contact angle thata liquid makes with a surface, wettability of the surface can becontrolled. In some embodiments, the higher the specific surface area ofa surface, the greater an effect on a contact angle of a fluid with thesurface. For example, for a particularly high wettability (e.g.hydrophilic) surface having a low contact angle with a fluid, providingthe surface with nanostructures, thus providing the surface with anincreased specific surface area with respect to the surface withoutnanostructures, can provide the surface with super high wettability(e.g. becoming superhydrophilic), having a lower contact angle with thefluid.

The term “specific surface area” as used herein refers to a totalsurface area per unit mass, cross-sectional area or another definedarea. For example, two surfaces can have different specific surfaceareas over a same macroscopic surface area, for example, by providing asurface with roughness. A first surface having a roughness which ishigher than a second surface is expected to have a higher specificsurface area than the second surface.

With reference to nanostructural features, the term “height” as usedherein refers to a height of a nanostructure from its base at a surfaceto its distal end.

With reference to nanostructural features, the term “distance” as usedherein refers to a distance between nanopillars, the distance can bemeasured from the center of the base of one nanostructure to the centerof the base of another nanostructure; or from the center of the distalend of one nanostructure to the center of the distal end of anothernanostructure.

With reference to nanostructural features, the term “diameter” as usedherein refers to a largest distance across the base of pillar. The term“diameter” is interchangeably with the term “width” with reference tonanostructural features as the nanostructure bases need not be circular,but can also be squares rectangles or irregularly shaped.

The term “transparent” as used herein refers to an ability of light of aparticular wavelength range to pass through a material/surface withoutscattering the light or with minimal scattering of the light.Accordingly, some amount of optical loss due to light scattering canlead to a translucent material/surface, which is a subset of transparentmaterials/surfaces according to the present disclosure. The term“transparency” as used herein refers to a feature of a material/surfacehaving the ability to allow light to pass through the material/surfacewithout scattering the light or with minimal scattering of the light.Thus, the term transparency can be used with reference to light of aparticular range of wavelengths, for example, visible light, infraredlight, ultraviolet light, etc.

With reference to nanostructural features, the term “wall roughness” asused herein refers to a roughness along walls of nanostructure inclusiveof all the surfaces of the nanostructures and is distinguishable fromthe term “surface roughness”. Wall roughness can be a result ofdifferent physical states of a surface material, for example anamorphous versus a crystalline form of a material, the amorphous formhaving a more smooth surface and the crystalline form having a roughersurface resulting from crystallites. As another example, wall roughnesscan be a result of porosity of a material, a higher porosity leading toa rougher surface than a lower porosity material. As another example,wall roughness can be a result of a applying a coating to the wallcoating comprising particles which leads to surface roughness.

The term “nanostructures” as used herein refers to a column-likestructure which protrudes from a surface to which the column-likestructure is substantially perpendicular. A nanostructure in the senseof the present disclosure encompasses, for example, nanoneedles,nanopillars, and nanocones. Nanostructures of the disclosure, comprisingnanopillars, nanoneedles, and nanocones, can be perpendicular to thesurface from top to bottom of the nanopillar (inclination angle 0) orcan be a cone-shaped or needle-like structure having a wider end at thesurface from which it protrudes and coming to a point away from saidsurface (inclination angle≠0). A nanostructure according to the presentdisclosure can range in size from 5 nm to 100 microns.

More particularly with respect to nanocones, nanocones can encompassnanocone-shaped structures wherein substantially inclined surfaces ofthe nanocones are concave or convex surfaces. Wettability (e.g.hydrophobicity or hydrophilicity) of a surface can be analyzed bymeasuring a contact angle of a water droplet on the surface. A surfacehaving a high contact angle between approximately 90-150° can be definedherein as having low wettability (e.g. a hydrophobic surface). A surfacehaving a higher contact angle between approximately 150-180° can bedefined herein as having super low wettability (e.g. a superhydrophobicsurface). A surface having a low contact angle between approximately20-60° can be classified as having high wettability (e.g. a hydrophilicsurface). A surface having a lower contact angle between approximately0-20° can be classified as having super high wettability (e.g. asuperhydrophilic surface).

In some embodiments, fluidic properties of a liquid can be controlled bya type of material of which the surface is comprised and nanostructuralfeatures of the surface. In particular, a surface comprisingnanostructures can be used to provide the surface with control fluidicproperties. More particularly, the configuration of the nanostructurescan provide the surface with control of fluidic properties based on anaverage height (h_(avg)), an average inclination angle (i_(avg)), and anaverage distance (d_(avg)) between the nanostructures.

In some embodiments, efficacy of particular configuration ofnanostructures, and in particular, nanostructures of a particularaverage height (h_(avg)), average inclination angle (i_(avg)), andhaving average distance (d_(avg)) between one another, can be estimatedby measuring contact angle that a surface comprising the nanostructuresmakes with a liquid and comparing this contact angle to a desiredcontact angle.

In some embodiments the surface is a rigid surface. A rigid surface inthe sense of the present disclosure comprises materials which cannotreadily be deformed by an applied pressure. For example, the rigidsurface can comprise a metal, ceramics, sapphire, fluoride optics, andglass. Metals according to the present disclosure can include, but arenot limited to a transition metal or transition metal alloy; any p-blockmetal or p-block metal alloy; and a semiconductor or semiconductoralloy. Glass according to the present disclosure include but are notlimited to boro-, fluoro-, phospho-, borophospho-, and alumino-silicate,other types of silicon-based glass, and metallic glasses.

Fogging can be minimized by either promoting wetting of condensates toavoid a formation of light scattering droplets or by decreasing thesurface wettability (e.g. increasing hydrophobicity), causing waterdroplets to bead up and rapidly run off. Wettability of a surface can bealtered by depositing thin films of varying wettability (e.g. ahydrophilic or a hydrophobic film) or by intentionally increasing itsroughness in a controlled fashion through incorporating nanostructuresthat promote or minimize a spreading of water.

In some embodiments, surface roughness has been shown to increase ordecrease wettability (e.g. to enhance hydrophobicity or hydrophilicity)by creating a larger contact area between a surface and a liquiddroplet. This change in contact angle changes the dynamics of aliquid-gas-solid equilibrium and can enhance wettability, or lackthereof. Thus, a slightly wettable (or slightly hydrophobic) surface canbecome a super wettable surface (or superhydrophobic) through additionof roughness or nanoscale surface textures, and liquids can attain ameta-stable state where droplets are suspended, creating an additionalliquid/solid/gas interface at the bottom of the droplet.

The term “resistance” as used herein refers to a rate at which wettingof a surface occurs for a particular fluid. For example, two differentsurfaces can have equal wettability with respect to a particular fluid,however, if one the surfaces has a greater resistance toward the fluidthen it can have a lower rate of wettability, even though a final stateof wetting for the surfaces can be the same.

In some embodiments, a nanostructuring of a surface can result in anincreased resistance between the surface and a fluid which contacts thesurface. Additionally, roughness on a nanostructure can provideadditional resistance between the surface and the fluid. Wallroughness/nanostructure roughness can be a result of different physicalstates of a surface material, for example an amorphous versus acrystalline form of a material, the amorphous form having a more smoothsurface and the crystalline form having a rougher surface resulting fromcrystallites; wall roughness can be a result of porosity of a material,a higher porosity leading to a rougher surface than a lower porositymaterial; and wall roughness can be a result of applying a coating tothe wall coating comprising particles which leads to surface roughness.

The distance between nanostructures, the height of the nanostructures,and the width of the nanostructures can create various resistances toeliminating the space created by the height, distance, width, andinclination angle/curvature. Thus, by controlling height, distance,width, and inclination angle/curvature, resistance of the surface to afluid can be controlled to result in different wetting characteristics.

In some embodiments, a substantially flat surface (non-nanostructured)having a lower wettability on a flat surface can exhibit increasedwettability by nanostructuring the surface according to embodiments ofthe disclosure. For example, if a substrate material inherently has alow wettability and thus substantially avoids wetting, providing thesurface with nanostructures can increase its wettability andaccordingly, a rate of wetting can be controlled. Additionally, byproviding a surface with nanostructures suitable for increasingwettability followed by providing a coating on the surface, in which thecoating itself inherently exhibits a low wettability (e.g. hydrophobic);the rate of wetting can be controlled based on opposing wettabilitycharacteristics (i.e. the coating having a low wettability (e.g.hydrophobic) and the nanostructured surface having a high wettability(e.g. hydrophilic)).

For example, a nanostructure configuration on a surface can beconfigured to increase or decrease wettability of the surface and acoating can be selected based on wettability of the coating (e.g. of thecoating being hydrophobic or hydrophilic). Selection of the surfaceconfiguration and the coating based on opposing wettabilitycharacteristics such that the coating has a lower wettability (e.g.hydrophobic), and can provide a means to control a rate of wetting ofthe coated, nanostructured surface.

For example, an R_(a) (RMS) of typical glass surfaces as produced, areless than approximately 0.5 nm. Surfaces of the present disclosurecomprising nanostructures can range from 1-400 nm which ismicroscopically rougher than typical glass surfaces while stillappearing macroscopically, as a smooth surface, that is, appearingsimilar to a corresponding surface prior to nanostructure fabrication.In some embodiments, the surfaces of the present disclosure comprisingnanostructures can be approximately 30 nm. The term “wetting” as usedherein refers to an ability of a liquid to maintain contact with a solidsurface and can be related to a ratio of a surface area of a liquiddroplet that is in contact with the solid surface to the total volume ofthe droplet, wherein the larger the contacted surface area to totalvolume, the greater the wetting.

In a consideration of light transmission in a nanostructured surface,both feature of distance and width are considered in connection with adesired size of the nanostructure to avoid light scattering. Forexample, both features being less than the wavelength for whichtransmission of light is desired can avoid light scattering.

The distance between nanostructures and the width of the nanostructurescan be configured to maintain transparency of a surface for a givenrange of wavelengths of light. For example, a ratio of approximately10:1 of wavelength to feature size can provide a higher transparency.However, a smaller ratio can be used with a small loss in transparency.

Thus, increasing a feature size with respect to a given wavelength oflight can decrease transparency of the surface with respect to thewavelength of light, while decreasing a feature size with respect to agiven wavelength of light can increase transparency of the surface withrespect to the wavelength of light.

Depending on wavelength of light for which passage of the light througha surface is desired, a target feature size can vary. For example, ifpassage of ultraviolet (UV) light though a surface is desired, giventhat UV light ranges from 10-400 nm, much smaller feature sizes can beused on a surface for which passage of UV light is desired than for asurface through which passage of visible light is desired given thatvisible light ranges from 400-750 nm. Thus, the smaller the wavelengthof light for which passage of the light through a surface is desired,the smaller the feature size can be. However, depending desired criteriafor transparency, dimensions of nanostructures having a size equal to alowest wavelength of a selected range of wavelengths can provide thenanostructured surface with approximately 10% loss of transparency.

While transparency of light of a certain wavelength can be aconsideration for some applications, if a surface for which control offluidic properties of a liquid is desired is for a non-transparentsurface, this consideration may not be necessary. For example, if thecontrol of fluidic properties is desired to achieve anti-foulingproperties on a boat hull, then the size and periodicity of thenanostructures can be selected based on a desired contact angle andpassage of light does not need to be considered.

In some embodiments, the height of a nanostructure can be selected basedon a wear rate. For example, nanostructures comprising surface on anoptical lens is likely subject to less wear than nanostructurescomprising surfaces on a boat hull or airplane. Accordingly, a largernanostructure height can be used in applications where wear is expected.Thus, with a larger nanostructure height, the nanostructures can weardown to a larger extent than shorter nanostructures before the controlof fluidic properties is affected.

In some embodiments, the transparency of a substrate is unaffected bythe etching treatments based on nanoparticle shadow masks. This isbecause the characteristic length scale of the roughness is at least 40times smaller than the wavelength of the transmitted visible light.

In some embodiments, a surface can be modified to boost the efficiencyof a solar cell. The device layers for an exemplary device of thisembodiment are schematically shown in FIG. 10. FIG. 10 comprises: panela (1005), illustrating a device schematic with layers to be sprayed on asolar cell commercial or previously fabricated panel; panel b (1010)showing an example band diagram illustrating the relationship betweenthe electron transport layer, hole transport layer and quantum dot (QD)absorber layers; panel c (1015) showing a simulated current-voltagecurve for a device with only the hole transport layer (HTL)/electrontransport layer (ETL), and a device with ETL/QD absorber/HTL.

The structure of FIG. 10 comprises a bottom electrode layer (1020)comprised, for example, of a transparent conductive oxide (TCO) and/or ametallic finger grid array or array of electrodes which is used forcurrent collection. On this bottom electrode (1020), anelectron-selective transparent contact layer (ETL, 1025) can bedeposited. Layer (1025) enables transport of electrons towards thebottom electrode (1020), and blocks the transport of holes from theactive semiconductor layer (1030) and top contact (1040) to the bottomelectrode (1020). Next, the quantum dot/microparticle layer or activesemiconductor layer (1030) can be deposited. This layer will absorb theincident solar photons. On the absorber layer (1030), a hole transportlayer (1035) can be deposited. This layer is analogous to the ETL, as itblocks electrons from flowing into the top contact. Subsequently, a topelectrode (1040) comprising, for example, a transparent conductive oxideand/or a metallic finger grid can be deposited.

FIG. 10, panel b shows an exemplary energy band diagram, with the HTL(1037), absorber (1042), and ETL (1047) conduction and valence bands.The diagram shows the conduction band through the device (1050, E_(C)),the valence band (1060, E_(V)), and Fermi level (1055, E_(F)). As knownto the person of ordinary skill in the art, electrons tend to movetowards lower energy states in the band diagram, while holes act asquasi-particles with an effective positive charge and tend to movetowards higher energy levels in the band diagram.

For the device to behave as desired, the difference in conduction bandsof the ETL and absorber layer must be small, while the difference invalence bands of the HTL and absorber layer must be small. There shouldalso be a significant energy barrier for the current between the HTL andETL. This is quantified by the exemplary I-V curves of the device inFIG. 10 panel c, with a curve for a device having only the barrierlayers (1070) and a curve for the device having barrier layers with theQD layer (1065). Specifically, it can be noted that the turn on voltageof the barrier layer only device (1075) is significantly larger than theturn on voltage for the other device (1080).

In some embodiments, the metal grids that comprise both the top andbottom electrode should be spaced as the metal grid of the previouslyfabricated photovoltaic (PV) panel (1045) on which the spray-onphotovoltaic device is added. This approach minimizes the photon lossdue to reflection by the metallic grid. Furthermore, the cells can besized with the same dimensions of the underlying PV panel. The materialoptions for some examples for each layer are listed in Table 1. Thethicknesses of the electron and hole transport layers can range, forexample, from 1 nm to 20 nm, while the absorber layer thicknesses canrange, for example, between 100 nm and 5 micrometers. In someembodiments, the QD layer may comprise a monolayer of nano ormicroparticles. For example, a monolayer of microparticles ormicrospheres having a diameter of about 1 micrometers could be used. Insome embodiments, the optimal thickness of the QD layer is about 1micrometer. A thickness of 1 micrometer can be realized by havingmultiple monolayers of nanoparticles, or by using a monolayer ofparticles with a diameter of 1 micrometer. In some embodiments, insteadof a photovoltaic panels other types of solar cells may be used.

In some embodiments, the layout of the exemplary device of FIG. 10 canfurther comprise another particle multilayer on the bottom of the PVpanel. This bottom attachment may be similar to the top structure, orhave a different structure. In these embodiments, the top structure, forexample comprising layers (1020,1025,1230,1035,1040) allows theabsorption of UV and visible light, while the PV panel could absorbnear-infrared light, and the bottom structure may absorb long-wavelengthinfrared light (longer wavelengths than those absorbed by the PV panel).The efficiency of a PV panel can be greatly increased by the inexpensivedeposition of particles on the top, bottom, or both top and bottomsurfaces. In some embodiments, layers (1040,1035) and (1020,1025) mayhave each a thickness of 10-100 nm, while the QD layer could have athickness of about 1 micrometer.

One possible advantage of using microspheres is the decrease in defectscompared to smaller nanoparticles, due to the fact that most defects arepresent on the surface of a particle, and larger particles have agreater volume to surface area ratio. In some embodiments, the devicemay comprise a QD layer with electrodes, without the ETL, the HTL, oreither the ETL and HTL. The structure may be fabricated by liquiddeposition as described in the present disclosure, or other methodsdescribed herein. In some embodiments, particles with differentdimensions may be used in the same QD layer—for example, a layer ofparticles having a first diameter, and a second layer of particles witha second diameter smaller than the first diameter. The layers with thelarger diameter may also be deposited in multiple layers, with thesmaller particles filling the spaces between the larger particles. Avoltage may be applied to the structure of FIG. 10, between electrodes(1020) and (1040), to optimize the load on the device. For example, thestructure may operate at 0.4-0.5 V. In some embodiments, the particlesmay be fabricated by ball milling of bulk materials, to createmicrospheres or nanoparticles.

TABLE 1 Electron Hole Bottom Top Transport Transport Absorber AbsorberLayer Layer Layer Layer TiO₂ GaP PbS InGaP WO₃ AlSb PbSe CdSe PbO ZnTePbTe CdZnTe MnTiO₃ NiO HgS AlGaAs SnO₂ AlCuO₂ HgCdTe CdSTe In₂O₃ MoO_(x)HgCdSe CdSSe Ca WO_(x) Bi₂Se₃ CsPbCl LiF_(x) CuPc Ge CsPbBr CsF_(x)CuSCN GaSb CsPbI KF_(x) CuO_(x):N InGaAs CsO_(x) V₂O_(x) MgF_(x) LaB₆

In some embodiments, attaching a top and bottom structure to a PV panelcan allow an overall efficiency, for example, of 25-50%, due to theincreased light absorption capacity across a larger spectrum ofwavelengths. In some embodiments, the efficiency of the top structureneeds to be at least 13% to not have detrimental effects on theefficiency of the underlying PV panel. The overall efficiency with onlythe top structure added to a PV panel may be, for example, about 25%. Inthe following, material choices for layers to add to PV panels aredescribed, with reference to Table 1. Table 1 lists exemplary materialsfor the optional ETL and HTL layers, as well as materials for thestructure to be deposited on top of a PV panel, and materials for thestructure to be deposited on the bottom of a PV panel. Other materialssuitable for the same purpose may be substituted for the materials ofTable 1.

Electron Transport Layer

The material options for the electron transport layer (ETL) can beseparated into three categories: 1. wide bandgap materials (e.g. with abandgap Eg>2 eV) which have a conduction band that matches up with theconduction band of the semiconductor absorber layer; 2. wide bandgapmaterials which when deposited as an amorphous structure, orsub-stoichiometrically, form defect states in the bandgap near theconduction band of the semiconductor absorber layer; 3. very low workfunction metallic materials. Of the materials listed for electrontransport layers (Table 1), TiO₂, PbO, SnO₂, In₂O₃ fall into the firstcategory, LiF_(x), CsF_(x), KF_(x), CsO, MgF_(x), fall into the secondcategory, and Ca, and LaB₆ fall into the third category.

Hole Transport Layer

Similarly to the ETL, the material options for the hole transport layer(HTL) can be separated into two categories: 1. wide bandgap materials(e.g. E_(g)>2 eV) which have a valence band that matches up with thevalence band of the semiconductor absorber layer; 2. wide bandgapmaterials, which when deposited as an amorphous structure, orsub-stoichiometrically, form defect states in the bandgap near thevalence band of the semiconductor absorber layer. Of the materialslisted for hole transport layers (Table 1), GaP, AlSb, ZnTe, NiO, andAlCuO₂, CuSCN, and CuPc fall into the first category, and MoO_(x),WO_(x), V₂O_(x), CuO_(x):N, fall into the second category.

Absorber Layers

The absorber layers for the top and bottom cell layers can be chosenaccording to the bandgap of the material. Specifically, in someembodiments the bandgap of the top cell may fall within the range from1.6 eV to 2.5 eV, while the bandgap of the bottom cell may fall withinthe range of 0.15 eV to 0.75 eV. Each of the binary and ternarysemiconductors for the top cell (Table 1) were chosen such that at leastone attainable mixture or compound exhibits a bandgap within the rangebetween 1.6 eV and 2.5 eV. Analogously, each of the materials chosen forthe bottom cell (Table 1) were chosen such that one phase of thosematerials exhibits a bandgap between 0.15 eV and 0.75 eV.

FIG. 11 illustrates an exemplary available power as a function ofwavelength, e.g. power available in the solar spectrum at a groundlocation. FIG. 12 illustrates an exemplary spectral efficiency for aGaInP cell (1205) and a Si solar panel (1210). It is possible to note aboost in efficiency in the wavelength range (1215) due to the differentabsorption and bandgaps of different semiconductor materials. By addinga top, bottom, or both a top and a bottom structure to a Si panel, it ispossible to boost the overall efficiency by combining differentabsorption profiles of different materials which have differentabsorption efficiencies.

FIG. 13 illustrates the efficiency for a Si cell (1310), as a constant,and the overall efficiency of the same Si cell with a 1.8 eV top cell(1305). The Si cell has an efficiency of 20%. The overall efficiency islower when the top cell has a low efficiency, but it increases as thetop cell efficiency is increased, surpassing the bare Si cell at thebreakeven point (1315). FIG. 14 illustrates an exemplary powerenhancement as the top cell efficiency is increased. FIG. 15 illustratessimilar data as FIG. 13, but for a 15% efficiency Si cell. FIG. 16illustrates similar data as FIG. 14, but for a 15% efficiency Si cell.It can be noted that, for a specific PV panel efficiency, there is aminimum efficiency required for the top structure, in order for theoverall efficiency to surpass the efficiency of the PV panel alone. Itcan be further noted that this concept can work for other panels besideSi panels.

FIG. 17 illustrates dark current-voltage (I-V) curves for a simulatedstructure having a top and bottom electrodes, with an ETL and HTL oneither side of an absorber layer, similarly as in FIG. 10. In FIG. 17,the absorber layer is CdSe, for example microspheres of CdSe. For dopinglevels of 10¹⁷, three curves are plotted for three different values ofti, a parameter indicating different recombination lifetimes: 10⁻¹¹(1705), 10⁻¹² (1710), and 10⁻¹³ (1715). Typical CdSe QDs normallyexhibit lifetimes between 10⁻¹⁰ and 10⁻¹² s. The data of FIG. 17 can becompared favourably to a state-of-the-art InGaP cell. Such a InGaP cellhas V_(oc)=1.4 V (V_(oc) is the open-circuit current), J_(sc)=15 mA(J_(sc) is the short-circuit current) and FF=0.88. The Fill Factor (FF)is a measure of quality of the solar cell. It is calculated by comparingthe maximum power to the theoretical power that would be output at boththe open circuit voltage and short circuit current together.

A structure as in FIG. 10, simulated in FIG. 17, could have V_(oc)between 0.8 V and 1 V. CdSe are known, currently to have spectralefficiencies of 40-60%, comparable to the InGaP state-of-the-art cell.Therefore, with a V_(oc)=0.8-1 V and J_(sc)=13 mA/cm², it would bepossible to achieve an efficiency of 13% for the QD structure.

FIG. 18 illustrates the power density for AM 1.5 G power (1805). Asknown to the person of ordinary skill in the art, AM 1.5 G is a standardset of values for power irradiated in a range of wavelength, used tosimulate solar power during development or testing of a solar paneldevice. FIG. 18 also illustrates the Si absorption cut-off (1815) andthe cumulative power density (1810). It can be noted that about 200 W/m²of power is not absorbed by the Si cell, representing about 20% ofincident AM 1.5 G power. By selecting a rear absorber, a bottomstructure as described in the present disclosure, with a bandgap around1800 nm (about 0.7 eV) it is possible to absorb about 150 W/m² of thepower that would be otherwise wasted by the solar panel.

FIGS. 19-20 illustrate current-voltage characteristics for a simulateddevice comprising a semiconductor with E_(g)=0.67 eV. In FIG. 19, threecurves are plotted: J-V dark (1905), J-V with irradiated light (1910)and power-voltage with irradiated light (1915). In FIG. 20, three curvesare plotted: J-V dark (2005), J-V with irradiated light (2010) andpower-voltage with irradiated light (2015). With an ideal PV cell, it ispossible to generate about 8 mW/cm² of power, a 40% boost in poweroutput for a 20% efficient Si panel. With a relatively low quality PVabsorber material cell, it is possible to generate about 1.9 mW/cm² ofpower, a 10% boost in power output for a 20% Si PV cell.

The implementation describe above is based on the fact that commonlyavailable solar panels are based on Si, due to the cost of productionand availability of the material. However, Si has poor spectralefficiency in the UV and visible spectrum, as well as in portions ofnear infrared. Therefore, it is possible to pair Si with a top absorberthat is efficient in capturing shorter wavelengths. By using both a topand bottom cell, it is also possible to capture shorter and longerwavelengths and therefore increase the efficiency of solar panels.

FIG. 22 illustrates an exemplary concept of spectral efficiency atdifferent wavelengths for Si and different absorbing materials to beused in the top and bottom of a PV panel, having different bandgaps. InFIG. 22, spectral efficiencies for different bandgaps (2205) between 1.4and 1.9 eV are schematically illustrated. A curve for the spectralefficiency of Si is also illustrated (2010). A first region (2215)illustrates the wavelength range where the spectral efficiency could beimproved by adding a top absorber to a Si panel. The middle region(2220) illustrates the wavelength range where Si could efficientlyabsorb light not absorbed by the top cell. The third region (2225)illustrates the wavelength range where a bottom cell attached to the SiPV panel could absorb longer wavelengths that are not as efficientlyabsorbed by Si. The first and third regions could also be termed tandemshort and tandem long, respectively, as the top absorber works in tandemwith Si at shorter wavelengths, while the bottom absorber works intandem with Si at longer wavelengths. Although the example of FIG. 22illustrates wavelengths up to 1200 nm, longer wavelengths may also beused, for example up to 1800 nm.

FIG. 23 illustrates an exemplary simulation for the overall tandemefficiency as a function of the top cell bandgap and the top cellfraction of detailed-balance efficiency, for a 20% efficient Si panelwith an absorber structure on top. Exemplary data points are indicatedfor GaInP, GaAs, CdTe and different perovskites. In FIG. 23, the tandemefficiency generally increases from left to right of the top cellfraction efficiency axis. In some embodiments, the top and bottomabsorbing structures can boost the efficiency of commercially availablesolar panels by up to 30%.

FIG. 24 illustrates an exemplary structure with a PV panel (2405) toabsorb light at 700-1000 nm, such as a Si panel, a top structure (2410)to absorb UV and visible light (e.g. CdSe QD or microspheres) and abottom structure (2415) to absorb at 1000-1300 nm (e.g. GaSb, InGaAs,etc). The structure may comprise: a transparent conductive oxideelectrode (2420); HTL (2425), QD layer (2430), ETL (2435), a bottomelectrode (2440), a PV panel (2445), a transparent conductive oxideelectrode (2450); HTL (2455), QD layer (2460), ETL (2465), a bottomelectrode (2470). It should be noted that other layers can be added, asdesired. For example, anti-reflection coatings may also be added as wellas electrode layers.

According to the present disclosure, the substrate surface can bemodified by additive processes such as, but not limited to, 3D printingof surface textures or bulk materials, nanoparticle attachment/layering,nanoscribing or similar writing of sacrificial or permanentmolds/templates for coatings, vapor deposition, and liquid phase and/orsupercritical phase deposition. The structures can be therefore createdby a large number of processes, some of which never use nanoparticles orALD. In other words, it is possible to 3D print the entire hierarchicaltexture, or mold the entire textures.

Alternatively, the substrate surface can be modified by subtractiveprocesses such as, but not limited to, wet (e.g., liquid phase orsupercritical phase) etching or dry (e.g., plasma or vapor) etching,and/or physical methods of removing materials from the substratesurface. In other embodiments, the substrate surface can be modified bya stamping or embossing process.

The various methods of surface modification (additive, subtractive,stamping, or embossing) can be used in isolation or in any combinationto produce the structure(s) and/or layer(s) to achieve the desiredphysical effects. As those skilled in the art will appreciate, thestructures and/or layers may be made from the same or differentmaterials.

In other exemplary embodiments, the structures or layers can bemonolithically fabricated as one continuous material with the substrate.Alternatively, the structures or layers can be added to the substratebefore, during, or after the substrate's fabrication. In other exemplaryembodiments, various techniques can be combined to create hierarchicalstructures or layers of a variety of materials to get the precisefunction and highest possible performance desired for any givenapplication. In other exemplary embodiments, 3D printing techniques ordirect writing processes can be used to produce functional structures orlayers in combination with or in isolation of the substrate.

As described above, silicon solar cells can be optimized by adding a topand bottom structure to absorb additional light when compared to a Sisolar cell without additional components. In some embodiments, anantireflection coating can also be added. For example, theantireflection structure could be added on top of layer (2420) in FIG.24, or incorporated in layer (2430) or (2425). In some embodiments, thePV panel already has an antireflection coating. For example, somepreviously fabricated PV panels may have an antireflection coating ontop—e.g. as part of the top surface of (2445). In this case, theapplication of structure (2410) can take into consideration theantireflection coating, in order to prevent any decrease in efficiency.In some embodiments, an air gap can therefore be advantageously added tothe top structure—e.g. structure (2410) in FIG. 24. For example, the airgap may be between (2445) and (2440)—between (2405) and (2410). If thegap between the top quantum dot cell (2410) and the previouslyfabricated silicon cell (2405) is larger than a few microns, theantireflection coating present on (2405) does not need to be modified,thus reducing technological requirements and costs. In some embodiments,small posts (pillars) may be used, to standoff the quantum dot cell ontop of the previously fabricated PV panel. For example, the posts mayhave a thickness in the millimeter or centimeter range. FIG. 21illustrates an example of such standoff spacers (2115) between a solarcell (2110) and a top structure (2105).

A back reflector can also be added at the bottom of the compositestructure. For example, a back reflector layer could be added belowlayer (2450), (2460) or (2470). Alternatively, a back reflector can alsobe added to the bottom of (2405), or may already be present in thepreviously fabricated PV panel. The back reflector can be configured toreflect any radiation not absorbed by the layers above, back towards theabsorbing layers. The back reflector can therefore increase the overallabsorption efficiency. In some embodiments, a wavelength selectablereflector can be used at the bottom of (2405), to ensure that only thevisible light and the radiation around the 1200 nm wavelength isreflected back towards the absorbing layers, while radiation with awavelength longer than 1200 nm is not reflected up, and is insteadabsorbed by the bottom structure (2415). For example, the back reflectormay comprise a Au film or a multilayer dielectric stack.

FIGS. 32-35 illustrate exemplary photo absorption structures on top of aPV panel. In particular, FIG. 32 illustrates a detail of the structureof FIG. 33, while FIG. 34 illustrates a detail of FIG. 35. Thestructures of FIGS. 32-35 illustrate photon management viananopatterning. These structures can reduce reflection across a widerange of angles, increase absorption for a given material thickness, andreduce material costs. The contact engineering enables the fabricationof optimal electron and hole selective contacts, maximizes open circuitvoltage for a given material quality, and mitigates the effect ofphysical defects such as pinholes. The carrier collection engineeringdecouples light absorption and collection directions, enables matchingof material carrier collection length with device structure, andincreases cell short circuit current and efficiency as compared toplanar structures.

These methods allow flexibility in the choice of absorber material, asthe spray-on technique enables a wide choice of materials with similardevice structures, significantly reducing cost as compared totraditional high temperature processing. The low-temperature processingenables direct deposition on commercially available panels. The layersof FIGS. 32-33 can correspond to those of FIG. 10 or FIG. 24: atransparent conductive oxide (3205); an electron transport layer (3210);an absorber layer (3215); a hole transport layer (3220); a transparentconductive oxide layer (3225), and, additionally, a photon managementlayer (3230). For example, the photon management layer is configured toreduce reflection, so that more photons are transmitted into theunderlying PV panel. FIG. 33 illustrates a structure comprising multipleelements as in FIG. 32. In the example of FIG. 32 and FIG. 33, thestructure has a jagged shape, formed by elements having a triangularcross-section. For example, the structure may comprise pyramids or maycomprise long lines extending normally to the plane of FIGS. 32-33,where each line has a triangular cross-section, forming a jagged gratingstructure. The inclination angles of the jagged elements may bedifferent for each layer, as visible for example in FIG. 33, where afirst inclination angle (3305) is different from a second inclinationangle (3310). In FIG. 33, the jagged structure of the top absorber(3315) is deposited on a previously fabricated PV panel (3320).

FIG. 34 illustrates another embodiment, where the structure comprisesrounded mounds instead of jagged elements as in FIG. 32. The layers ofFIGS. 34-35 correspond to those of FIG. 32: a transparent conductiveoxide (3405); an electron transport layer (3410); an absorber layer(3415); a hole transport layer (3420); a transparent conductive oxidelayer (3425), and a photon management layer (3430). In some embodiments,the structure of FIG. 35 may comprise an array of nanopillars, or a beamgrating with the beams extending normally to the plane of FIG. 35. Thedimensions and distance between elements in FIG. 33 or 35 may be chosenso as to control the physical properties of the structure, as describedabove in the present disclosure.

The photon management layers in FIGS. 32 and 34, (3230) and (3430) areexamples of layers that can be used for photon management. In someembodiments, the photon management layers may comprise structures suchas the jagged profile in FIG. 32, or the pillars in FIG. 34. In otherembodiments, these layers may also be flat layers without a complexstructure. The photon and minority carrier management structural layercan serve two purposes: improvement of device interaction with photons,and reduction of minority carrier recombination. By creating nanoscalestructures on the top surface of the photon management layer, this layercan act as a broadband, wide-angle, anti-reflection structure. Theanti-reflection structure minimizes reflection of normally incidentsolar photons by the underlying solar cell structures. Theanti-reflection property can apply to the UV, visible, and near IRphoton wavelength ranges. The anti-reflection structure can also reducereflection for off-normal solar photons.

The mechanism by which the anti-reflection structure reduces reflectionis through a gradation of the effective index of refraction from the airto the solar cell underneath it. This gradation occurs when thedimensions of the structures are in the sub-wavelength regime withrespect to the incident photon wavelength. For example, to have aneffect in the UV band, the structures would have dimensions less thanthe wavelength in the UV range (e.g. 250 nm). As a consequence, theelectric field of the incident electromagnetic waves can simultaneouslyinteract with the solar cell material and air. If, for example, astructure is surrounded by air, the effective index of refraction of thelayer comprising the structure surrounded by air can be calculated as asn_(eff)(f)=n_(air)*f+n_(mat)*(1−f), where n_(eff)(f) is the effectiverefractive index felt by the photon in the mixed region, and f is thefraction of the plane orthogonal to the direction of photon travel thatis air. The index of refraction of air and the material is given byn_(air) and n_(mat), respectively. Thus, by creating structures withcontinuously varying fractions f, it is possible to grade the refractiveindex. In other words, the refractive index will not be uniform acrossthe depth of the material, but will have a gradient which can becontrolled by changing the shape of the structure. For example, if thestructure has pillars with a specific spacing, by keeping the heightconstant and decreasing the spacing, a greater fraction of the mixedlayer will be occupied by the structure material instead of air. As aconsequence, the effective refractive index will weigh the contributionfrom the refractive index of the material more than that of air,compared to the case with increased spacing between pillars. The widthof the pillars could also be changed, or a slope could be introduced toform truncated pyramids or cones. The slope angle could be changed for asimilar effect.

The person of ordinary skill in the art will understand that, forstructures not in contact with air but covered by additional materiallayers, such as in FIGS. 32 and 34, the same averaging principle for theeffective refractive index is valid, by substituting the refractiveindex of air by the refractive index of the material layers depositedconformally to the structure.

Therefore, the gradient for the effective index can be controlled byvarying the geometrical dimension and shape of the anti-reflectionstructure, as well as choosing appropriate materials with specificrefractive indexes.

Another photon management effect of the absorber structure is to allowcoupling of the incident photons into multiple, local, guided modes andresonances. The result of this coupling is an increase of absorption perunit volume of material in the absorber layer. Several mechanisms canenable this feature. For example, by creating structured top and bottomsurfaces, local broadband resonances are created due to the internalreflection of light from the top surface of the solar cell which occurinto multiple internal modes. These resonances can then increase theabsorption of photons which couple into them. This feature allows areduction in the amount of material used, which in turn enables carriercollection engineering as described herein. Specifically, by creatingfeature sizes that are between 0.25 to 0.5 times the wavelengthrepresenting the midpoint of the spectrum of interest, we can expectenhancements in absorption by up to 2×. For solar materials, thewavelengths corresponding to the bandgap energy of the semiconductor(Eg) up to Eg+0.1 eV are absorbed the most weakly. Thus, to enhance theoptical absorption of this range by up to 2×, devices with lateralfeature sizes between 0.25*1.24/(Eg+0.05) to 0.5*1.24/(Eg+0.05) can beused. The vertical feature size can be 1 to 2 times the absorptionlength of the semiconductor in the wavelength range between Eg andEg+0.05 eV. The absorption length can be defined as the length lightmust travel in the semiconductor structure before 1/e of the incidentlight remains unabsorbed.

Specifically, these resonances can be observed through electromagneticsimulations of the film and observation of the photon generation rate inthe material with computational simulations. In planar materials, thegeneration rate decays monotonically in a direction orthogonal to thelight facing surface, and is uniform in directions parallel to thesurface facing the incident light. However, the resonances created bynanostructuring cause the photon generation rates to locally increase atthe location of the resonance in the film. This can be observed throughsimulation as a deviation from the generation rate profiles of theplanar material in both the parallel and orthogonal directions from thelight-facing surface.

As an example, if the semiconductor bandgap energy is 1.8 eV,corresponding to a wavelength of approximately 690 nm, then thestructures may have lateral dimensions ranging from approximately 160 nmup to 340 nm. If the semiconductor has an absorption depth of 400 nm atthe wavelength of interest, the structure can have heights ranging from400 nm up to 800 nm. Due to the feature size being of the same order ofmagnitude as the photon wavelength, the interactions between the photonsand the structured features are rigorously described by fullthreedimensional finite difference time domain electromagneticsimulations. However, the effect is created due to the interaction ofthe photon with these non-planar geometries. Specifically, theresonances described here are created by incident photons interactingwith these sub-wavelength structures, which may be pyramidal, conical,or cylinders, and scattering from their initial direction. When multiplescattering events occur, interference between the photons cause localresonances to occur. As the films are absorptive, these resonances occurwhen the path length of photons in the material is larger than thephoton scattering lengths. If the path length of photons in the materialbefore absorption is significantly shorter than the scattering length,then the photons will be absorbed before multiple scattering events canoccur, and no resonances will occur. By engineering the dimensions ofthe structures as previously described, both periodic and randomstructures will create these resonances within the wavelength range ofinterest, e.g. 400 nm-700 nm.

The carrier collection engineering aspect of this structure emerges fromthe proximity of the electron and hole collection layers to every pointin the device. In standard planar photovoltaics, the photon absorptionand carrier collection both occur in the same direction. However, bygenerating local resonances, and through the use of nanostructuredmaterials, it is possible to decouple the photon absorption and minoritycarrier directions. As a result, the maximum distance any minoritycarrier must travel in the device before being collected can be reduced.The short circuit current of the cell will therefore improve. In view ofthe above, the photon management layer can also be considered a minoritycarrier management layer. Due to the change in the local photongeneration rate, it is possible to engineer such films to have a largerfraction of the photons absorbed closer to a carrier collecting surfaceor layer. This enables the losses of generated minority carriers to beengineered and minimized by designing the structure to maximally absorbphotons and generate minority carriers near carrier-collecting surfacessuch as the electron transport layer and hole transport layer.

In view of the above, if the characteristic dimensions of thenanotextures are carefully controlled, the scattering length of thephotons is lower than the photon path length. The photons, therefore,have a chance to be scattered at the nanostructures a few times as theytravel to the base of the nanostructure, for example to the base of thepyramidal or rod-shaped elements. The increased scattering increasestheir effect chance of being collected. If the structures are too smallor too large, multiple scattering events do not occur before the photonmakes its way through the absorber. It can be noted that, in the presentdisclosure, a surface can be engineered by forming a structure formed byelements with typical dimensions less than half an incident wavelength.These wavelength is the blocked by the surface. As a consequence, morephotons of the incident wavelength will scatter back up away from thesurface. Similarly, the absorber layer can be formed by elements havingtypical dimensions less than half a wavelength of the photons to bescattered back towards the solar cells absorbing layers.

In some embodiments, the aspect ratio, or height, of the elements canincrease the scattering of photons back towards the absorbing layers ofthe solar cell. In some embodiments, the scattering effect is maximizedif the elements of the structures have a height of about 1 micrometer.For example, the pillars of layer (3430) in FIG. 34 or the pyramids oflayer (3230) in FIG. 32 can have a height of about 1 micrometer toadvantageously maximize scattering of photons towards the absorbinglayers of the solar cell, above.

In some embodiments, the photon management layer can be realized byfirst fabricating a high aspect ratio ETL (e.g. an aspect ratio between5:1 and 10:1 and lateral dimension of 100 nm-200 nm). Normally, thelithography steps involved in fabricating such a high aspect ratio layerwould increase the cost substantially. However, by using any of themethods described in the present disclosure, this high aspect ratiolayer can be fabricated at a greatly reduced cost. For example, thestructure may be formed by building monolayers of particles. Thestructure may also be formed by using particles as an etch mask, asdescribed in the present disclosure. The structure may also befabricated by building monolayers of particles and fusing the particlestogether. Once the high aspect ratio structure is fabricated, a uniformand conformal layer of quantum-dot particles can be coated on the highaspect ratio structure. The absorber layer of QDs may comprise amonolayer of particles, or multiple layers, as described in the presentdisclosure. Therefore, the fabrication of a high aspect ratio structurecoated with nanoparticles can be realized due to the methods describedin the present disclosure, at an affordable cost.

As known to the person of ordinary skill in the art, current solarinstallations are primarily based on single junction solar cells. Thepresent disclosure describes methods that works with present daytechnologies, and improves their power output with minimal requiredchanges to the overall cell and panel architecture. In some embodiments,the methods and structures of the present disclosure can be integratedthrough post processing, independently of solar manufacturers, or at theend of the manufacturing process, before encapsulation. These methodsalso work with multijunction cells.

In some embodiments, the first functional group is selected from thegroup consisting of: —CH₃, —OH, —NH₂, an ester group, an aldehyde group,an amide group, and a nitrile group, and the first fluid is selectedfrom the group consisting of: trimethyl-aluminum, a chloride compound, afluoride compound, an organometallic compound, and an acetylacetonatecompound, hexane mixed with trimethyl-aluminum, hexane mixed with achloride compound, hexane mixed a fluoride compound, hexane mixed anorganometallic compound, hexane mixed an acetylacetonate compound, ametal-organic chemical vapour deposition precursor, and an atomic layerdeposition precursor. Other mixtures comprising different solvents thanhexane may also be used. In some embodiments, the surface of theparticles might comprise a functional group, obviating the need toprepare the particles' surface with a precursor. Alternatively, thesurface to be coated may comprise these functional groups, and thereforeonly the particles' surface needs to be prepared. For example, if ananoparticle inherently has —OH on the surface, it may be unnecessary toprepare its surface with a —OH functional group, since the particle'smaterial already comprises it. In this example, it may be possible toprepare the surface to be coated, for example with TMA, and then sprayor otherwise attach the particles to the treated surface, without aparticle preparation step.

In some embodiments, the particles bonded on a surface may have the samechemical composition as the substrate. In some embodiments, theparticles may be coated with the same material as the substrate. Inthese cases, the outer region of the particles will be the same as thesubstrate, while the internal region of the particles may be different.In some embodiments, particle mixtures may include a majority ofparticles of the same material as the substrate, and a minority ofparticles that have a different material. This different material mayhave a different etching rate compared to the material of the substrate.For example, the minority of particles may etch at a faster rate thanthe substrate, or at a slower rate than the substrate. In someembodiments, using the same materials for the particles and thesubstrate can render the coating process (of the particles to thesubstrate) easier. In some embodiments, the etching process can also besimplified, by using the same material for both the particles and thesubstrate, or a different material with a different etching rate. Insome embodiments, the roughness of the structures can be controlled toform hierarchical structures.

In some embodiments, forming a first monolayer of particles on thesurface is by forming less than one monolayer by providing a flux ofnanoparticles insufficient to completely saturate the surface. In someembodiments, forming a first monolayer of particles on the surface is byforming more than one monolayer, comprising a first monolayer and atleast one other particle in a partial second monolayer, by flushing inpart particles in excess of the first monolayer. In some embodiments,the first plurality of particles comprises particles having differentsizes, shape or composition. In some embodiments, the first plurality ofparticles has a different size, shape or composition than the secondplurality of particles. In some embodiments, if differently-sizedparticles are used together, the smaller particles may attach to thebigger particles, as well as to the substrate, in gaps between thebigger particles. In some embodiments, if different materials are usedfor the particles, these particles can be used as shadow masks thanks totheir differential etching rate. For example, by using dissimilarmaterials, it is possible to pattern a surface due to the differentialetch rates. For example, if a mixture of SiO₂ and Al₂O₃ nanoparticles issprayed on a surface, the particles would etch very differently influorine etchants. The different etching rates can result in inherentpatterning.

Matrixes comprising metal and dielectric nanoparticles may also be usedto fabricate meta materials, for example metamaterials having exoticproperties, such as metamaterials used for cloaking applications torender objects invisible or less visible. Particles can also be used tocreate materials with a negative index of refraction.

In some embodiments, nanoparticles can be sintered with lasers or heatafter application to surfaces. Particles can also be used to fabricateantifogging optics for environmental chambers for LED and solar cellcharacterization in high humidity environments. In some embodiments, theparticles and substrates have been described as being covalently bonded.However, in other embodiments, the particles and substrate can bephysically interacting, for example through electrostatic or van derWaals forces. Therefore, the descriptions of the present disclosure canbe referred to also as physically interacting instead of covalentlybonded. In the present disclosure, therefore, covalently bonded can besubstituted for physically interacting, as appropriate.

In some embodiments, the control of different properties of the surface,such as transparency and reflectivity at specific wavelengths, can bedescribed as control of the effective refractive index of each layer.The refractive index of a layer comprising different materials iseffectively controlled by the type of material as well as the relativedimensions and contributions of each material to the layer's volume. Forexample, by varying the shape of a structure, the effective refractiveindex of that structure can be controlled.

In some embodiments a low temperature can be used for the depositionprocess to minimize gradients in surface tension during evaporation ofthe relevant fluids. The structure of the present disclosure may also befabricated by building monolayers of particles and fusing the particlestogether, for example by raising the temperature, or by forming chemicalbonds between particles. In this way, metamaterials can be fabricated,by using similar or dissimilar particles.

The various embodiments described above are provided by way ofillustration only and should not be construed to limit the presentdisclosure. Those skilled in the art will readily recognize variousmodifications and changes that may be made to the present disclosurewithout following the example embodiments and applications illustratedand described herein, and without departing from the true spirit andscope of the present disclosure.

A number of embodiments of the disclosure have been described.Nevertheless, it will be understood that various modifications may bemade without departing from the spirit and scope of the presentdisclosure. Accordingly, other embodiments are within the scope of thefollowing claims.

The examples set forth above are provided to those of ordinary skill inthe art as a complete disclosure and description of how to make and usethe embodiments of the disclosure, and are not intended to limit thescope of what the inventor/inventors regard as their disclosure.

Modifications of the above-described modes for carrying out the methodsand systems herein disclosed that are obvious to persons of skill in theart are intended to be within the scope of the following claims. Allpatents and publications mentioned in the specification are indicativeof the levels of skill of those skilled in the art to which thedisclosure pertains. All references cited in this disclosure areincorporated by reference to the same extent as if each reference hadbeen incorporated by reference in its entirety individually.

It is to be understood that the disclosure is not limited to particularmethods or systems, which can, of course, vary. It is also to beunderstood that the terminology used herein is for the purpose ofdescribing particular embodiments only, and is not intended to belimiting. As used in this specification and the appended claims, thesingular forms “a,” “an,” and “the” include plural referents unless thecontent clearly dictates otherwise. The term “plurality” includes two ormore referents unless the content clearly dictates otherwise. Unlessdefined otherwise, all technical and scientific terms used herein havethe same meaning as commonly understood by one of ordinary skill in theart to which the disclosure pertains.

What is claimed is:
 1. A method comprising: determining a first lateraldimension of each element in a structure on a surface, the structurecomprising a plurality of elements, the determining based on a firstphysical characteristic of the structure, the first lateral dimensionbeing in a horizontal orientation relative to the surface; determining asecond lateral dimension of each element, the second lateral dimensionbeing perpendicular to the first lateral dimension and in a horizontalorientation relative to the surface; determining a height of eachelement based on a second physical characteristic of the structure, theheight being in a vertical orientation relative to the surface;determining a spacing between the elements based on the first and secondphysical characteristics; fabricating the structure comprising theplurality of elements; defining a plurality of patterned features on theplurality of elements, the patterned features having dimensions smallerthan any of the first lateral dimension, the second lateral dimension,and the height of each element, the patterned features based on a thirdphysical characteristic of the structure; determining a first wavelengthrange comprising wavelengths between a first maximum wavelength and afirst minimum wavelength, the first minimum wavelength being less thanthe first maximum wavelength; determining a second wavelength rangecomprising wavelengths between a second maximum wavelength and the firstmaximum wavelength, the second maximum wavelength being greater than thefirst maximum wavelength; functionalizing the structure with aself-saturated monolayer of a first functional group; functionalizing afirst plurality of particles with a second functional group, the secondfunctional group chosen so as to form a covalent or ionic bond with thefirst functional group; and forming a monolayer of the first pluralityof particles on the structure, wherein: the structure comprising theplurality of elements and the plurality of patterned features ismonolithic, the first physical characteristic is transparency toelectromagnetic radiation, and the first lateral dimension and thesecond lateral dimension are less than half the first maximumwavelength.
 2. The method of claim 1, wherein the first and secondlateral dimensions are equal to each other.
 3. The method of claim 1,wherein the second physical characteristic is reflectivity toelectromagnetic radiation, and further comprising determining a thirdwavelength range, wherein determining a height of each element is toincrease the reflectivity of the surface at the third wavelength range.4. The method of claim 1, further comprising determining an inclinationangle for lateral surfaces of each element of the structure, accordingto a contact angle for a droplet contacting the structure, a smallercontact angle corresponding to a hydrophilic property for the structure,and a higher contact angle corresponding to a hydrophobic property forthe structure.
 5. The method of claim 1, further comprising selecting adiameter and material of the particles to emit electromagnetic radiationin a wavelength range between 7.5 and 8.5 micrometers.
 6. The method ofclaim 1, further comprising selecting a diameter and material of theparticles to absorb infrared radiation.
 7. The method of claim 1,further comprising selecting a diameter and material of the particlesbased on the first and second physical characteristics.
 8. The method ofclaim 1, wherein the first wavelength range is UV electromagneticradiation, and the second wavelength range is visible electromagneticradiation.
 9. The method of claim 1, wherein the surface is a flexiblesubstrate.
 10. The method of claim 1, wherein the flexible substrate isa clothing substrate.
 11. The method of claim 1, wherein determining thefirst lateral dimension, the second lateral dimension, and the height ofeach element comprises selecting a shape for each element.
 12. Themethod of claim 11, wherein the shape is selected from the groupconsisting of: a parallelepiped, a pyramid, a cone, a cube, a beam, anellipsoid and a sphere.
 13. The method of claim 12, further comprisingselecting a roughness value for a surface of each element based on thefirst and second physical characteristics.
 14. The method of claim 1,wherein forming a monolayer of the first plurality of particlescomprising spraying onto the surface the first plurality of particles ina fluid dispersion.
 15. The method of claim 14, wherein the particlesare polarizable along an axis, and forming a monolayer of the firstplurality of particles comprises applying an electric and/or magneticfield during spraying to orient the particles along the axis, therebydepositing the first plurality of particles oriented along the axis andobtaining a polarization-sensitive surface.
 16. The method of claim 1,wherein the first plurality of particles comprises particles selectedfrom the group consisting of: metals, metal oxides, metal nitrides,carbon nanotubes, buckyballs, and architectured 3D nanostructures, andthe surface comprises a material selected from: glass, ceramics,plastics, polymers, textiles, semiconductors, metals, 3D printedmaterials, and 3D architectured materials.
 17. The method of claim 4,wherein determining an inclination angle according a hydrophobicproperty is limitedly to a sub-region of the structure, so that for anenvironmental humidity range which will cause fogging, the sub-regionwill not fog.
 18. The method of claim 1, wherein the second physicalcharacteristic is selected from the group consisting of: reflectivity toincident electromagnetic radiation, transparency to incidentelectromagnetic radiation, antifogging, hydrophobicity, sensitivity topolarization of incident electromagnetic radiation, absorption ofincident electromagnetic radiation, blocking of incident electromagneticradiation, blocking of incident electromagnetic radiation in a firstwavelength range and transparency to incident electromagnetic radiationin a second wavelength range different from the first wavelength range,emissivity to incident electromagnetic radiation, antifrosting, oilrepellency, water repellency, absorption to incident electromagneticradiation, ability to emit electrons, ability to amplify and emitelectrons, and combinations thereof.
 19. The method of claim 1, whereinthe first lateral dimension, the second lateral dimension, the height ofeach element and the spacing between elements are each less than 10micrometers.
 20. The method of claim 1, wherein forming a monolayer ofthe first plurality of particles comprises dipping the surface in afluid dispersion comprising the first plurality of particles.
 21. Amethod comprising: determining a first lateral dimension of each elementin a structure on a surface based on a desired transparency of thestructure to incident electromagnetic radiations, the structurecomprising a plurality of elements, the first lateral dimension being ina horizontal orientation relative to the surface and being less thanhalf of a wavelength of an electromagnetic radiation to be blocked bythe structure; determining a height of each element based on a desiredreflectivity for the incident electromagnetic radiation, the heightbeing in a vertical orientation relative to the surface; determining aspacing between the elements based on the desired transparency andreflectivity; fabricating the structure comprising the plurality ofelements; and defining a plurality of patterned features on theplurality of elements, the patterned features having dimensions smallerthan any of the first lateral dimension, the second lateral dimension,and the height of each element, the patterned features based on a thirdphysical characteristic of the structure, wherein the structurecomprising the plurality of elements and the plurality of patternedfeatures is monolithic.
 22. The method of claim 21, further comprisingdetermining a second lateral dimension of each element based on adesired polarization characteristic of the structure, the second lateraldimension being perpendicular to the first lateral dimension and in ahorizontal orientation relative to the surface, the second lateraldimension having a different value than the first lateral dimension. 23.A structure comprising: an array of pillars on a surface, each pillarhaving a first lateral dimension x, a second lateral dimension z, and aheight y; a plurality of patterned features on each pillar of theplurality of pillars, each patterned feature of the plurality ofpatterned feature having a width between 5 nm and 40 nm, and a depthbetween 5 nm and 40 nm; and a monolayer of particles covering eachpillar, wherein x is between 50 nm and 250 nm, thereby blockingultraviolet radiation, y is between 120 nm and 180 nm, thereby reducingreflected radiation, each particle of the monolayer has a diameter lessthan 200 nm and is made of a material capable of absorbing infraredradiation.
 24. The structure of claim 23, wherein z is at least threetimes x.
 25. The structure of claim 23, wherein z is less than 400 nm.26. The structure of claim 23, wherein y is greater than x by at least 3times, thereby enabling viewing angle selectivity.